Methods of copolymerizing ethylene and isobutylene and polymers made thereby

ABSTRACT

New ligands, compositions, metal-ligand complexes and arrays with pyridyl-amine ligands are disclosed that catalyze the polymerization of monomers into polymers. Certain of these catalysts with hafnium metal centers have high performance characteristics, including higher comonomer incorporation into ethylene/olefin copolymers, where such olefins are for example, 1-octene, isobutylene or styrene. Certain of the catalysts are particularly effective at polymerizing propylene to high molecular weight isotactic polypropylene in a solution process at a variety of polymerization conditions.

This application claims the benefit of U.S. Provisional PatentApplication No. 60/246,781, filed Nov. 7, 2000 and the benefit of U.S.Provisional Patent Application No. 60/301,666, filed Jun. 28, 2001, bothof which are incorporated herein by reference for all purposes.

FIELD OF THE INVENTION

The present invention relates to ligands, complexes, compositions and/orcatalysts that provide enhanced olefin polymerization capabilities basedon a substituted pyridyl amine structure and hafnium. The invention alsorelates to methods of polymerization. The invention also relates toisotactic polypropylene and methods of preparing isotacticpolypropylene.

BACKGROUND OF THE INVENTION

Ancillary (or spectator) ligand-metal coordination complexes (e.g.,organometallic complexes) and compositions are useful as catalysts,additives, stoichiometric reagents, monomers, solid state precursors,therapeutic reagents and drugs. Ancillary ligand-metal coordinationcomplexes of this type can be prepared by combining an ancillary ligandwith a suitable metal compound or metal precursor in a suitable solventat a suitable temperature. The ancillary ligand contains functionalgroups that bind to the metal center(s), remain associated with themetal center(s), and therefore provide an opportunity to modify thesteric, electronic and chemical properties of the active metal center(s)of the complex.

Certain known ancillary ligand-metal complexes and compositions arecatalysts for reactions such as oxidation, reduction, hydrogenation,hydrosilylation, hydrocyanation, hydroformylation, polymerization,carbonylation, isomerization, metathesis, carbon-hydrogen activation,carbon-halogen activation, cross-coupling, Friedel-Crafts acylation andalkylation, hydration, dimerization, trimerization, oligomerization,Diels-Alder reactions and other transformations.

One example of the use of these types of ancillary ligand-metalcomplexes and compositions is in the field of polymerization catalysis.In connection with single site catalysis, the ancillary ligand typicallyoffers opportunities to modify the electronic and/or steric environmentsurrounding an active metal center. This allows the ancillary ligand toassist in the creation of possibly different polymers. Group 4metallocene based single site catalysts are generally known forpolymerization reactions. See, generally, “Chemistry of CationicDicyclopentadienyl Group 4 Metal-Alkyl Complexes”, Jordan, Adv.Organometallic Chem., 1991, Vol. 32, pp. 325-153 and “StereospecificOlefin Polymerization with Chiral Metallocene Catalysts”, Brintzinger,et al., Angew. Chem. Int. Ed. Engl., 1995, Vol. 34, pp. 1143-1170, andthe references therein, all of which is incorporated herein byreference.

However, those of skill in the art of single site catalysis appreciatethat there may be substantial differences in performance betweendifferent metal centers. For example, U.S. Pat. No. 5,064,802 disclosesa broad category of mono-cyclopentadienyl ligand catalysts with a broaddisclosure of useful metals, and U.S. Pat. No. 5,631,391 morespecifically discloses that titanium metal centers offer performanceadvantages with respect to the same or similar ligands. Additionally,Coates, et al., Angew. Chem. Int. Ed., 2000, vol. 39, pp. 3626-3629describes the unpredictable nature of olefin polymerization catalyststructure-activity relationships. Thus, references that describe, forexample, groups 3-13 and the lanthanides, for example in U.S. Pat. No.6,103,657, are not of adequate performance indicators of all that iswithin the scope of what is allegedly described. Moreover, as those ofskill in the art appreciate, differences in ligand substituentstypically polymerize different monomers at different performances underdifferent polymerization conditions, and discovering those specificsremains a challenge.

One application for metallocene catalysts is producing isotacticpolypropylene. An extensive body of scientific literature examinescatalyst structures, mechanism and polymers prepared by metallocenecatalysts. See, e.g., Resconi et al., “Selectivity in PropenePolymerization with Metallocene Catalysts,” Chem. Rev. 2000, 100,1253-1345 and G. W. Coates, “Precise Control of PolyolefinStereochemistry Using Single-Site Metal Catalysts,” Chem. Rev. 2000,100, 1223-1252 and the references sited in these review articles. Seealso, U.S. Pat. No. 5,026,798 that reports a mono-cyclopentadienylmetallocene for the production of isotactic polypropylene. Isotacticpolypropylene has historically been produced with heterogeneouscatalysts that may be described as a catalyst on a solid support (e.g.,titanium tetrachloride and aluminum alkyls on magnesium dichloride).This process typically uses hydrogen to control the molecular weight andelectron-donor compounds to control the isotacticity. See also EP0622380, U.S. Pat. Nos. 4,297,465, 5,385,993 and 6,239,236.

Given the extensive research activities with respect to metallocenecatalysts, there is continued interested in the next generation ofnon-cyclopentadienyl ligands for olefin polymerization catalystsproviding attractive alternatives. See, e.g., “The Search forNew-Generation Olefin Polymerization Catalysts: Life beyondMetallocenes”, Gibson, et al., Angew. Chem. Int. Ed., 1999, vol. 38, pp.428-447; Organometallics 1999, 18, pp. 3649-3670. Recently, such systemshave been discovered, see, e.g., U.S. Pat. Nos. 6,103, 657 and5,637,660. For isotactic polypropylene, bis-amide catalysts have beendisclosed in U.S. Pat. No. 5,318,935 and amidinate catalysts have beendisclosed in WO 99/05186. See also U.S. Pat. No. 6,214,939.

There remains a need for the discovery and optimization ofnon-cyclopentadienyl based catalysts for olefin polymerization, and inparticular for certain polymers, such as isotactic polypropylene andethylene-alpha-olefin copolymers. For a solution polymerizationmethodology, this need may be acute in view of the lack of versatilecatalysts for the preparation of isotactic polypropylene at commerciallyacceptable temperatures. Indeed, new polymer properties are disclosedherein for isotactic polypropylene, ethylene-styrene copolymers andethylene-isobutylene copolymers.

SUMMARY OF THE INVENTION

This invention discloses surprising enhanced catalytic performances forolefin polymerization when certain combinations of ligands and hafniummetal precursors are employed. This invention also discloses surprisingenhanced catalytic performances for olefin polymerization when certainmetal complexes are employed in a catalyst, including 2,1 metalcomplexes and 3,2 metal complexes. In addition, some of the ligandsemployed herein are themselves novel.

In some embodiments, this invention discloses both the preferred use ofa hafnium metal center and certain pyridyl-amine ligands. Suchcombinations lead to new ligand-metal complexes, catalyst compositionsand processes for the polymerization of olefins, diolefins, or otherpolymerizable monomers. In particular, copolymers of ethylene andanother monomer may be prepared with controlled incorporation of theother monomer (e.g., 1-octene, isobutylene, or styrene) into the polymerbackbone. In some embodiments, this control is adjusted so that theolefin incorporation is considered to be high with respect to polymerscurrently known or commercially available. Also in particular, propylenemay be polymerized into very high molecular weight isotacticpolypropylene. Thus, polymers having novel, improved or desiredproperties may be prepared using the catalysts and processes of thisinvention.

More specifically, in some embodiments, the use of a hafnium metal hasbeen found to be preferred as compared to a zirconium metal forpyridyl-amine ligand catalysts. A broad range of ancillary ligandsubstituents may accommodate the enhanced catalytic performance. Thecatalysts in some embodiments are compositions comprising the ligand andmetal precursor, and optionally may additionally include an activator,combination of activators or activator package.

The invention disclosed herein additionally includes catalystscomprising ancillary ligand-hafnium complexes, ancillaryligand-zirconium complexes and optionally activators, which catalyzepolymerization and copolymerization reactions, particularly withmonomers that are olefins, diolefins or other unsaturated compounds.Zirconium complexes, hafnium complexes, compositions or compounds usingthe disclosed ligands are within the scope of this invention. Themetal-ligand complexes may be in a neutral or charged state. The ligandto metal ratio may also vary, the exact ratio being dependent on thenature of the ligand and metal-ligand complex. The metal-ligand complexor complexes may take different forms, for example, they may bemonomeric, dimeric or higher orders thereof.

For example, suitable ligands useful in this invention may becharacterized by the following general formula:

wherein R¹ is a ring having from 4-8 atoms in the ring generallyselected from the group consisting of substituted cycloalkyl,substituted heterocycloalkyl, substituted aryl and substitutedheteroaryl, such that R¹ may be characterized by the general formula:

where Q¹ and Q⁵ are substituents on the ring ortho to atom E, with Ebeing selected from the group consisting of carbon and nitrogen and withat least one of Q¹ or Q⁵ being bulky (defined as having at least 2atoms). Q″_(q) represents additional possible substituents on the ring,with q being 1, 2, 3, 4 or 5 and Q″ being selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, substituted heteroalkyl,heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl,phosphino, amino, thio, seleno, halide, nitro, and combinations thereof.T is a bridging group selected group consisting of —CR²R³— and —SiR²R³—with R² and R³ being independently selected from the group consisting ofhydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substitutedhetercycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphino, amino, thio,seleno, halide, nitro, and combinations thereof. J″ is generallyselected from the group consisting of heteroaryl and substitutedheteroaryl, with particular embodiments for particular reactions beingdescribed herein.

Also for example, in some embodiments, the ligands of the invention maybe combined with a metal precursor compound that may be characterized bythe general formula Hf(L)_(n) where L is independently selected from thegroup consisting of halide (F, Cl, Br, I), alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, heteroalkyl, substitutedheteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy,hydroxy, boryl, silyl, amino, amine, hydrido, allyl, diene, seleno,phosphino, phosphine, carboxylates, thio, 1,3-dionates, oxalates,carbonates, nitrates, sulphates, ethers, thioethers and combinationsthereof; and optionally two L groups may be linked together in a ringstructure. n is 1, 2, 3, 4, 5, or 6.

In another aspect of the invention, a polymerization process isdisclosed for monomers. The polymerization process involves subjectingone or more monomers to the catalyst compositions or complexes of thisinvention under polymerization conditions. The polymerization processcan be continuous, batch or semi-batch and can be homogeneous, supportedhomogeneous or heterogeneous. Another aspect of this invention relatesto arrays of ligands, metal precursors and/or metal-ligand complexes.These arrays are useful for the high speed or combinatorial materialsscience discovery or optimization of the catalyst compositions orcomplexes disclosed herein.

These catalysts comprising ancillary ligand-metal complexes orcompositions comprising metal precursors and ligands and, optionally,activators are particularly effective at polymerizing α-olefins (such aspropylene, 1-butene, 1-pentene, 1-hexene, is 1-heptene, 1-octene, andstyrene), copolymerizing ethylene with α-olefins (such as propylene,1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and styrene), andcopolymerizing ethylene with 1,1-disubstituted olefins (such asisobutylene). These compositions might also polymerize monomers thathave polar functionalities in homopolymerizations or copolymerizations.Also, diolefins in combination with ethylene and/or α-olefins or1,1-disubstituted olefins may be copolymerized. The new catalystcompositions can be prepared by combining a hafnium precursor with asuitable ligand and, optionally, an activator or combination ofactivators. This invention discloses a novel class of catalysts andimproved method for preparing isotactic polypropylene. The catalyst isuseful for polymerizing a wide variety of polymerizable monomers.

In particular, a method of producing isotactic polypropylene is in asolution process is disclosed and is surprisingly tunable. In oneaspect, the temperature of the solution polymerization process can beincreased, which generally decreases the molecular weight, butsurprisingly, while maintaining a relatively high isotacticity of thepolypropylene and while maintaining a relatively high melting point forthe polypropylene. In another aspect, the temperature of the solutionprocess can be increased without the molecular weight of thepolypropylene dropping so low to levels that are unacceptable forcertain commercial applications.

In certain aspects, it has been discovered that certain ligands complexto the metal resulting in novel complexes. In one aspect, the 3,2metal-ligand complexes of this invention may be generally characterizedby the following formula:

where M is zirconium or hafnium;

R¹ and T are defined above;

J′″ being selected from the group of substituted heteroaryls with 2atoms bonded to the metal M, at least one of those atoms being aheteroatom, and with one atom of J′″ is bonded to M via a dative bond,the other through a covalent bond; and L¹ and L² are independentlyselected from the group consisting of halide, alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, heteroalkyl, substitutedheteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy,hydroxy, boryl, silyl, amino, amine, hydrido, allyl, diene, seleno,phosphino, phosphine, carboxylates, thio, 1,3-dionates, oxalates,carbonates, nitrates, sulphates, ethers, thioethers and combinationsthereof; and optionally the L groups may be linked together in a ringstructure.

In another aspect, a solution process to prepare isotactic polypropyleneis provided comprising adding a catalyst and propylene monomer to areactor and subjecting the contents to polymerization conditions, wherethe temperature of the solution process is at least 110° C. andpolypropylene is produced that has a weight average molecular weight ofat least 100,000, without a drop off in tacticity value (i.e.,crystallinity index).

Thus, it is a feature of this invention to use hafnium-ligand complexesas polymerization catalysts with enhanced performance.

It is an object of this invention to polymerize olefins and unsaturatedmonomers with hafnium-ligand complexes. It is also an object of thisinvention to polymerize olefins and unsaturated monomers withcompositions including substituted pyridyl amine ligands and hafniummetal precursors.

It is still a further object of this invention to polymerize olefins andunsaturated monomers with the hafnium-ligand complexes that additionallycomprise an activator or combination of activators.

It is also an object of this invention to use non-metallocene group 4complexes as polymerization catalysts for the production of isotacticpolypropylene.

It is a further object of this invention to polymerize olefins andunsaturated monomers with a catalyst comprised of metal complexescomprising 3,2 ligands.

Further objects and aspects of this invention will be evident to thoseof skill in the art upon review of this specification.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts Table 1, which lists compounds that may be useful forsynthesizing the ligands in this invention.

FIG. 2 depicts Table 2, which lists other compounds that may be usefulfor synthesizing the ligands in this invention.

FIG. 3 depicts Table 3, which shows the ligands and results fromexamples, below, using the Hf metal precursor.

FIG. 4 depicts Table 4, which shows the ligands and results fromcomparative examples, below, using the Zr metal precursor.

DETAILED DESCRIPTION OF THE INVENTION

The inventions disclosed herein include metal complexes andcompositions, which are useful as catalysts for polymerizationreactions.

As used herein, the phrase “characterized by the formula” is notintended to be limiting and is used in the same way that “comprising” iscommonly used. The term “independently selected” is used herein toindicate that the R groups, e.g., R¹, R², R³, R⁴, and R⁵ can beidentical or different (e.g. R¹, R², R³, R⁴ , and R⁵ may all besubstituted alkyls or R¹ and R² may be a substituted alkyl and R³ may bean aryl, etc.). Use of the singular includes use of the plural and viceversa (e.g., a hexane solvent, includes hexanes). A named R group willgenerally have the structure that is recognized in the art ascorresponding to R groups having that name. The terms “compound” and“complex” are generally used interchangeably in this specification, butthose of skill in the art may recognize certain compounds as complexesand vice versa. For the purposes of illustration, representative certaingroups are defined herein. These definitions are intended to supplementand illustrate, not preclude, the definitions known to those of skill inthe art.

“Hydrocarbyl” refers to univalent hydrocarbyl radicals containing 1 toabout 30 carbon atoms, preferably 1 to about 24 carbon atoms, mostpreferably 1 to about 12 carbon atoms, including branched or unbranched,saturated or unsaturated species, such as alkyl groups, alkenyl groups,aryl groups, and the like. “Substituted hydrocarbyl” refers tohydrocarbyl substituted with one or more substituent groups, and theterms “heteroatom-containing hydrocarbyl” and “heterohydrocarbyl” referto hydrocarbyl in which at least one carbon atom is replaced with aheteroatom.

The term “alkyl” is used herein to refer to a branched or unbranched,saturated or unsaturated acyclic hydrocarbon radical. Suitable alkylradicals include, for example, methyl, ethyl, n-propyl, i-propyl,2-propenyl (or allyl), vinyl, n-butyl, t-butyl, i-butyl (or2-methylpropyl), etc. In particular embodiments, alkyls have between 1and 200 carbon atoms, between 1 and 50 carbon atoms or between 1 and 20carbon atoms.

“Substituted alkyl” refers to an alkyl as just described in which one ormore hydrogen atom bound to any carbon of the alkyl is replaced byanother group such as a halogen, aryl, substituted aryl, cycloalkyl,substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl,halogen, alkylhalos (e.g., CF₃), hydroxy, amino, phosphido, alkoxy,amino, thio, nitro, and combinations thereof. Suitable substitutedalkyls include, for example, benzyl, trifluoromethyl and the like.

The term “heteroalkyl” refers to an alkyl as described above in whichone or more hydrogen atoms to any carbon of the alkyl is replaced by aheteroatom selected from the group consisting of N, O, P, B, S, Si, Sb,Al, Sn, As, Se and Ge. This same list of heteroatoms is usefulthroughout this specification. The bond between the carbon atom and theheteroatom may be saturated or unsaturated. Thus, an alkyl substitutedwith a heterocycloalkyl, substituted heterocycloalkyl, heteroaryl,substituted heteroaryl, alkoxy, aryloxy, boryl, phosphino, amino, silyl,thio, or seleno is within the scope of the term heteroalkyl. Suitableheteroalkyls include cyano, benzoyl, 2-pyridyl, 2-furyl and the like.

The term “cycloalkyl” is used herein to refer to a saturated orunsaturated cyclic non-aromatic hydrocarbon radical having a single ringor multiple condensed rings. Suitable cycloalkyl radicals include, forexample, cyclopentyl, cyclohexyl, cyclooctenyl, bicyclooctyl, etc. Inparticular embodiments, cycloalkyls have between 3 and 200 carbon atoms,between 3 and 50 carbon atoms or between 3 and 20 carbon atoms.

“Substituted cycloalkyl” refers to cycloalkyl as just describedincluding in which one or more hydrogen atom to any carbon of thecycloalkyl is replaced by another group such as a halogen, alkyl,substituted alkyl, aryl, substituted aryl, cycloalkyl, substitutedcycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, heteroaryl,substituted heteroaryl, alkoxy, aryloxy, boryl, phosphino, amino, silyl,thio, seleno and combinations thereof. Suitable substituted cycloalkylradicals include, for example, 4-dimethylaminocyclohexyl,4,5-dibromocyclohept-4-enyl, and the like.

The term “heterocycloalkyl” is used herein to refer to a cycloalkylradical as described, but in which one or more or all carbon atoms ofthe saturated or unsaturated cyclic radical are replaced by a heteroatomsuch as nitrogen, phosphorous, oxygen, sulfur, silicon, germanium,selenium, or boron. Suitable heterocycloalkyls include, for example,piperazinyl, morpholinyl, tetrahydropyranyl, tetrahydrofuranyl,piperidinyl, pyrrolidinyl, oxazolinyl and the like.

“Substituted heterocycloalkyl” refers to heterocycloalkyl as justdescribed including in which one or more hydrogen atom to any atom ofthe heterocycloalkyl is replaced by another group such as a halogen,alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl,substituted heteroaryl, alkoxy, aryloxy, boryl, phosphino, amino, silyl,thio, seleno and combinations thereof. Suitable substitutedheterocycloalkyl radicals include, for example, N-methylpiperazinyl,3-dimethylaminomorpholinyl and the like.

The term “aryl” is used herein to refer to an aromatic substituent,which may be a single aromatic ring or multiple aromatic rings that arefused together, linked covalently, or linked to a common group such as amethylene or ethylene moiety. The aromatic ring(s) may include phenyl,naphthyl, anthracenyl, and biphenyl, among others. In particularembodiments, aryls have between 1 and 200 carbon atoms, between 1 and 50carbon atoms or between 1 and 20 carbon atoms. In some embodimentsherein, multi-ring moieties are substituents and in such an embodimentthe multi-ring moiety can be attached at an appropriate atom. Forexample, “naphthal” can be 1-naphthyl or 2-naphthyl; “anthracenyl” canbe 1-anthracenyl, 2-anthracenyl or 9-anthracenyl; and “phenanthrenyl”can be 1-phenanthrenyl, 2-phenanthrenyl, 3-phenanthrenyl,4-phenanthrenyl or 9-phenanthrenyl.

“Substituted aryl” refers to aryl as just described in which one or morehydrogen atom bound to any carbon is replaced by one or more functionalgroups such as alkyl, substituted alkyl, cycloalkyl, substitutedcycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, halogen,alkylhalos (e.g., CF₃), hydroxy, amino, phosphido, alkoxy, amino, thio,nitro, and both saturated and unsaturated cyclic hydrocarbons which arefused to the aromatic ring(s), linked covalently or linked to a commongroup such as a methylene or ethylene moiety. The common linking groupmay also be a carbonyl as in benzophenone or oxygen as in diphenyletheror nitrogen in diphenylamine.

The term “heteroaryl” as used herein refers to aromatic or unsaturatedrings in which one or more carbon atoms of the aromatic ring(s) arereplaced by a heteroatom(s) such as nitrogen, oxygen, boron, selenium,phosphorus, silicon or sulfur. Heteroaryl refers to structures that maybe a single aromatic ring, multiple aromatic ring(s), or one or morearomatic rings coupled to one or more non-aromatic ring(s). Instructures having multiple rings, the rings can be fused together,linked covalently, or linked to a common group such as a methylene orethylene moiety. The common linking group may also be a carbonyl as inphenyl pyridyl ketone. As used herein, rings such as thiophene,pyridine, isoxazole, pyrazole, pyrrole, furan, etc. or benzo-fusedanalogues of these rings are defined by the term “heteroaryl.”

“Substituted heteroaryl” refers to heteroaryl as just describedincluding in which one or more hydrogen atoms bound to any atom of theheteroaryl moiety is replaced by another group such as a halogen, alkyl,substituted alkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, boryl, phosphino, amino, silyl, thio,seleno and combinations thereof. Suitable substituted heteroarylradicals include, for example, 4-N,N-dimethylaminopyridine.

The term “alkoxy” is used herein to refer to the —OZ¹ radical, where Z¹is selected from the group consisting of alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, heterocylcoalkyl, substitutedheterocycloalkyl, silyl groups and combinations thereof as describedherein. Suitable alkoxy radicals include, for example, methoxy, ethoxy,benzyloxy, t-butoxy, etc. A related term is “aryloxy” where Z¹ isselected from the group consisting of aryl, substituted aryl,heteroaryl, substituted heteroaryl, and combinations thereof. Examplesof suitable aryloxy radicals include phenoxy, substituted phenoxy,2-pyridinoxy, 8-quinalinoxy and the like.

As used herein the term “silyl” refers to the —SiZ¹Z²Z³ radical, whereeach of Z¹, Z², and Z³ is independently selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,heterocycloalkyl, heterocyclic, aryl, substituted aryl, heteroaryl,substituted heteroaryl, alkoxy, aryloxy, amino, silyl and combinationsthereof.

As used herein the term “boryl” refers to the —BZ¹Z² group, where eachof Z¹ and Z² is independently selected from the group consisting ofhydrogen, alkyl, substituted alkyl, cycloalkyl, heterocycloalkyl,heterocyclic, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, amino, silyl and combinations thereof.

As used herein, the term “phosphino” refers to the group —PZ¹Z², whereeach of Z¹ and Z² is independently selected from the group consisting ofhydrogen, substituted or unsubstituted alkyl, cycloalkyl,heterocycloalkyl, heterocyclic, aryl, substituted aryl, heteroaryl,silyl, alkoxy, aryloxy, amino and combinations thereof.

As used herein, the term “phosphine” refers to the group: PZ¹Z²Z³, whereeach of Z¹, Z³and Z² is independently selected from the group consistingof hydrogen, substituted or unsubstituted alkyl, cycloalkyl,heterocycloalkyl, heterocyclic, aryl, substituted aryl, heteroaryl,silyl, alkoxy, aryloxy, amino and combinations thereof.

The term “amino” is used herein to refer to the group —NZ¹Z², where eachof Z¹ and Z² is independently selected from the group consisting ofhydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl andcombinations thereof.

The term “amine” is used herein to refer to the group: NZ¹Z²Z³, whereeach of Z¹, Z² and Z² is independently selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl,aryl (including pyridines), substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl and combinations thereof.

The term “thio” is used herein to refer to the group —SZ¹, where Z¹ isselected from the group consisting of hydrogen, alkyl, substitutedalkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl and combinations thereof.

The term “seleno” is used herein to refer to the group —SeZ¹, where Z¹is selected from the group consisting of hydrogen, alkyl, substitutedalkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl and combinations thereof.

The term “saturated” refers to lack of double and triple bonds betweenatoms of a radical group such as ethyl, cyclohexyl, pyrrolidinyl, andthe like.

The term “unsaturated” refers to the presence one or more double andtriple bonds between atoms of a radical group such as vinyl, acetylide,oxazolinyl, cyclohexenyl, acetyl and the like.

Other abbreviations used herein include: “Pr^(i)” to refer to isopropyl;“Bu^(t)” to refer to tertbutyl; “Me” to refer to methyl; and “Et” torefer to ethyl.

Ligands

Suitable ligands useful in this invention can be characterized broadlyas monoanionic ligands having an amine and a heteroaryl or substitutedheteroaryl group. The ligand substituents for particular monomers aredetailed near the end of this section. The ligands of the invention maybe characterized by the following general formula:

wherein R¹ is generally selected from the group consisting of alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl,substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl,aryl, substituted aryl, heteroaryl, substituted heteroaryl andcombinations thereof. In many embodiments, R¹ is a ring having from 4-8atoms in the ring generally selected from the group consisting ofsubstituted cycloalkyl, substituted heterocycloalkyl, substituted aryland substituted heteroaryl, with R¹ being characterized by the generalformula:

where Q¹ and Q⁵ are substituents on the ring ortho to atom E, with Ebeing selected from the group consisting of carbon and nitrogen and withat least one of Q¹ or Q⁵ being bulky (defined as having at least 2non-hydrogen atoms). Q¹ and Q⁵ are independently selected from the groupconsisting of alkyl, substituted alkyl, cycloalkyl, substitutedcycloalkyl, aryl, substituted aryl and silyl, but provided that Q¹ andQ⁵ are not both methyl. Q″_(q) represents additional possiblesubstituents on the ring, with q being 1, 2, 3, 4 or 5 and Q″ beingselected from the group consisting of hydrogen, alkyl, substitutedalkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substitutedheteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl,silyl, boryl, phosphino, amino, thio, seleno, halide, nitro, andcombinations thereof T is a bridging group selected group consisting of—CR²R³— and —SiR²R³— with R² and R³ being independently selected fromthe group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, substituted heteroalkyl,heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl,phosphino, amino, thio, seleno, halide, nitro, and combinations thereof.J″ is generally selected from the group consisting of heteroaryl andsubstituted heteroaryl, with particular embodiments for particularreactions being described herein.

In a more specific embodiment, suitable ligands useful in this inventionmay be characterized by the following general formula:

wherein R¹ and T are as defined above and each of R⁴, R⁵, R⁶ and R⁷ isindependently selected from the group consisting of hydrogen, alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl,substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl,aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl,aryloxyl, silyl, boryl, phosphino, amino, thio, seleno, halide, nitro,and combinations thereof. Optionally, any combination of R¹, R², R³ andR⁴ may be joined together in a ring structure.

In certain more specific embodiments, the ligands in this invention maybe characterized by the following general formula:

wherein Q¹, Q⁵, R², R³, R⁴, R⁵, R⁶ and R⁷ are as defined above. Q², Q³and Q⁴ are independently selected from the group consisting of hydrogen,alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substitutedhetercycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphino, amino, thio,seleno, nitro, and combinations thereof.

In other more specific embodiments, the ligands of this invention andsuitable herein may be characterized by the following general formula:

wherein R¹, R², R³, R⁴, R⁵, and R⁶ are as defined above. In thisembodiment the R⁷ substituent has been replaced with an aryl orsubstituted aryl group, with R¹⁰, R¹¹, R¹² and R¹³ being independentlyselected from the group consisting of hydrogen, halide, alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl,substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl,aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy,aryloxy, silyl, boryl, phosphino, amino, thio, seleno, nitro, andcombinations thereof; optionally, two or more R¹⁰, R¹¹, R¹² and R¹³groups may be joined to form a fused ring system having from 3-50non-hydrogen atoms. R¹⁴ is selected from the group consisting ofhydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substitutedhetercycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio,seleno, halide, nitro, and combinations thereof.

In still more specific embodiments, the ligands in this invention may becharacterized by the general formula:

wherein R²-R⁶, R¹⁰-R¹⁴ and Q¹-Q⁵ are all as define above.

In certain embodiments, R² is preferably hydrogen. Also preferably, eachof R⁴ and R⁵ is hydrogen and R⁶ is either hydrogen or is joined to R⁷ toform a fused ring system. Also preferred is where R³ is selected fromthe group consisting of benzyl, phenyl, naphthyl, 2-biphenyl, t-butyl,2-dimethylaminophenyl (2-(NMe₂)—C₆H₄—),2-methoxyphenyl (2-MeO—C₆H₄—),anthracenyl, mesityl, 2-pyridyl, 3,5-dimethylphenyl, o-tolyl andphenanthrenyl. Also preferred is where R¹ is selected from the groupconsisting of mesityl, 4-isopropylphenyl (4-Pr^(i)—C₆H₄—), napthyl,3,5-(CF₃)₂—C₆H₃—, 2-Me-napthyl, 2,6-(Pr^(i))₂—C₆H₃—, 2-biphenyl,2-Me-4-MeO—C₆H₃—, 2-Bu^(t)—C₆H₄—, 2,5-(Bu^(t))₂—C₆H₃—,2-Pr^(i)-6-Me—C₆H₃—, 2-Bu^(t)-6-Me—C₆H₃—, 2,6-Et₂—C₆H₃— or2-sec-butyl-6Et—C₆H₃—. Also preferred is where R⁷ is selected from thegroup consisting of hydrogen, phenyl, napthyl, methyl, anthracenyl,phenanthrenyl, mesityl, 3,5-(CF₃)₂—C₆H₃—, 2-CF₃—C₆H₄—, 4-CF₃—C₆H₄—,3,5-F₂—C₆H₃—, 4-F—C₆H₄—, 2,4—F₂—C₆H₃—, 4-(NMe₂)—C₆H₄—, 3-MeO—C₆H₄—,4-MeO—C₆H₄—, 3,5-Me₂—C₆H₃—, o-tolyl, 2,6-F₂—C₆H₃— or where R⁷ is joinedtogether with R⁶ to form a fused ring system, e.g., quinoline. In somepreferred embodiment, R⁴, R⁵ and R⁶ are each independently selected fromthe group consisting of alkyl, aryl, halide, alkoxy, aryloxy, amino, andthio.

In some embodiments, Q¹ and Q⁵ are, independently, selected from thegroup consisting of —CH₂R¹⁵, —CHR¹⁶R¹⁷ and methyl, provided that notboth Q¹ and Q⁵ are methyl. In these embodiments, R¹⁵ is selected fromthe group consisting of alkyl, substituted alkyl, aryl and substitutedaryl. R¹⁶ and R¹⁷ are independently selected from the group consistingof alkyl, substituted alkyl, aryl and substituted aryl; and optionallyR¹⁶ and R¹⁷ are joined together in a ring structure having from 3-50non-hydrogen atoms.

Also optionally, two or more R⁴, R⁵, R⁶, R⁷groups may be joined to forma fused ring system having from 3-50 non-hydrogen atoms in addition tothe pyridine ring, e.g. generating a quinoline group. In theseembodiments, R³ is selected from the group consisting of aryl,substituted aryl, heteroaryl, substituted heteroaryl, primary andsecondary alkyl groups, and —PY₂ where Y is selected from the groupconsisting of aryl, substituted aryl, heteroaryl, and substitutedheteroaryl.

Optionally within above formulas IV and V, R⁶ and R¹⁰ may be joined toform a ring system having from 5-50 non-hydrogen atoms. For example, ifR⁶ and R¹⁰ together form a methylene, the ring will have 5 atoms in thebackbone of the ring, which may or may not be substituted with otheratoms. Also for example, if R⁶ and R¹⁰ together form an ethylene, thering will have 6 atoms in the backbone of the ring, which may or may notbe substituted with other atoms. Substituents from the ring can beselected from the group consisting of halide, alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, heteroalkyl, substitutedheteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy,silyl, boryl, phosphino, amino, thio, seleno, nitro, and combinationsthereof.

Specific examples of ligands within the scope of these formulas include:

In certain embodiments, the ligands are novel compounds and those ofskill in the art will be able to identify such compounds from the above.One example of the novel ligand compounds, includes those compoundsgenerally characterized by formula (III), above where R² is selectedfrom the group consisting of hydrogen, alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, aryl, and substituted aryl; and R³is a phosphino characterized by the formula —PZ¹Z², where each of Z¹ andZ² is independently selected from the group consisting of hydrogen,substituted or unsubstituted alkyl, cycloalkyl, heterocycloalkyl,heterocyclic, aryl, substituted aryl, heteroaryl, silyl, alkoxy,aryloxy, amino and combinations thereof. Particularly preferredembodiments of these compounds include those where Z¹ and Z² are eachindependently selected from the group consisting of alkyl, substitutedalkyl, cycloalkyl, heterocycloalkyl, aryl, and substituted aryl; andmore specifically phenyl; where Q¹, Q³, and Q⁵ are each selected fromthe group consisting of alkyl and substituted alkyl and each of Q² andQ⁴ is hydrogen; and where R⁴, R⁵, R⁶ and R⁷ are each hydrogen.

Certain embodiments of these ligands are preferred for thepolymerization of certain monomers. In any of the above formulas I, II,III, IV or V, for the production of isotactic polypropylene it is anaspect of this invention that R² cannot be the same group as R³, leadingto a chiral center on the carbon atom from which R² and R³ stem. Thus,generally, R³ may be selected from the group consisting of hydrogen,halide, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substitutedhetercycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio,seleno, nitro, and combinations thereof, but it has also been learnedthat for isotactic polypropylene production R³ is aryl, substitutedaryl, heteroaryl or substituted heteroaryl. In more specific embodimentsfor isotactic polypropylene production R³ is selected from the groupconsisting of benzyl, phenyl, naphthyl, 2-biphenyl,2-dimethylaminophenyl, 2-methoxyphenyl, anthracenyl, mesityl, 2-pyridyl,3,5-dimethylphenyl, o-tolyl, or phenanthrenyl. Also here, R¹ is selectedfrom the group consisting of 2,6-(Pr^(i))₂—C₆H₃—, 2-Pr^(i)-6-Me—C₆H₃—,2,6-Et₂—C₆H₃— or 2-sec-butyl-6-Et—C₆H₃—.

Also for isotactic polypropylene production it is preferred that withinformula A, above, it is currently preferred that Q¹ and Q⁵ are alkyl,substituted alkyl, heteroalkyl, substituted heteroalkyl, silyl,cycloalkyl, or substituted cycloalkyl, provided that Q¹ and Q⁵ are notboth methyl. Here also, Q¹ and Q⁵ can be, independently, selected fromthe group consisting of —CH₂R¹⁵, —CHR¹⁶R¹⁷ and methyl, provided that notboth Q¹ and Q⁵ are methyl. In a more specific embodiment for isotacticpolypropylene production, it is currently preferred that Q¹ and Q⁵ areboth isopropyl; or both ethyl; or both sec-butyl; or Q¹ is methyl and Q⁵is isopropyl; or Q¹ is ethyl and Q⁵ is sec-butyl. Even morespecifically, with these Q¹ and Q⁵ preferences, R¹ is either

or

with the above definitions of the variables applying.

For isotactic polypropylene production it is preferred R⁷ is aryl,substituted aryl, heteroaryl or substituted heteroaryl, and morespecifically R⁷ is phenyl, napthyl, mesityl, anthracenyl orphenanthrenyl. Thus, most preferably, formulas IV and V above apply toisotactic polypropylene production, with it currently being preferredthat R¹⁰, R¹¹, R¹², R¹³ each hydrogen; or one or more of R¹⁰, R¹¹, R¹²,R¹³ are methyl, fluoro, trifluoromethyl, methoxy, or dimethylamino; orwhere R¹⁰ and R¹¹ are joined to form a benzene ring and R¹² and R¹³ areeach hydrogen (thus forming a napthyl group with the existing phenylring).

Specific ligands that are preferred for the production of crystallinepolypropylene are:

For the production of ethylene-styrene copolymers, there are differentpreferences depending on the type of polymer that is desired. In someembodiments, it is preferred that the ligands of either of formulas II,III, IV or V is used, particularly with R⁷ selected from the groupconsisting of aryl, substituted aryl, heteroaryl, and substitutedheteroaryl. Specific ligands that are preferred for ethylene-styrenecopolymer production are:

For the production of ethylene-1-octene copolymers, it is preferred thatthe ligands of either of formulas II, III, IV or V is used, with eitheror both of R³ and/or R⁷ being independently selected from the groupconsisting of aryl, substituted aryl, heteroaryl, and substitutedheteroaryl. Specific ligands that are preferred for ethylene-1-octenecopolymer production are:

For the production of ethylene-isobutylene copolymers, it is currentlypreferred that R² and R³ are either both hydrogen or R² is hydrogen andR³ is aryl, substituted aryl or substituted alkyl. It is also importantfor ethylene-isobutylene copolymerization that R⁷ is hydrogen. Specificligands useful in this invention for the production ofethylene-isobutylene copolymers include:

The ligands of the invention may be prepared using known procedures.See, for example, Advanced Organic Chemistry, March, Wiley, N.Y. 1992(4^(th) Ed.). Specifically, the ligands of the invention may be preparedusing the two step procedure outlined in Scheme 1.

In Scheme 1, the * represents a chiral center when R² and R³ are notidentical; also, the R groups have the same definitions as above.Generally, R³M² is a nucleophile such as an alkylating or arylating orhydrogenating reagent and M² is a metal such as a main group metal, or ametalloid such as boron. The alkylating, arylating or hydrogenatingreagent may be a Grignard, alkyl, aryl-lithium or borohydride reagent.Scheme 1, step 2 first employs the use of complexing reagent.Preferably, as in the case of Scheme 1, magnesium bromide is used as thecomplexing reagent. The role of the complexing reagent is to direct thenucleophile, R³M², selectively to the imine carbon. Where the presenceof functional groups impede this synthetic approach, alternativesynthetic strategies may be employed. For instance, ligands whereR³=phosphino can be prepared in accordance with the teachings of U.S.Pat. Nos. 6,034,240 and 6,043,363. In addition, tetra-alkylhafniumcompounds or tetra-substituted alkylhafnium compounds ortetra-arylhafnium compounds or tetra-substituted arylhafnium compoundsmay be employed in step 2, in accordance with the teachings of U.S. Pat.No. 6,103,657, which is incorporated herein by reference. Scheme 2further describes a synthesis process:

In scheme 2, h=1 or 2 and the bromine ions may or may not be bound tothe magnesium. The effect of the complexation is to guide the subsequentnucleophilic attack by R³M² to the imine carbon. Thus complexation maylead to a more selective reaction that may increase the yield of thedesired ancillary ligands. Using this technique, selectivity isgenerally greater than about 50%, more preferably greater than about 70%and even more preferably greater than about 80%. Complexation may beparticularly useful for the preparation of arrays of ancillary ligandsof the type disclosed in the invention, where R³ is a variable in thepreparation of the ancillary ligand array. As shown in Scheme 2 by the*, where R² and R³ are different, this approach also leads to theformation of a chiral center on the ancillary ligands of the invention.Under some circumstances R³M² may be successfully added to the imine inthe absence the complexing reagent. Ancillary ligands that possesschirality may be important in certain olefin polymerization reactions,particularly those that lead to a stereospecific polymer, see“Stereospecific Olefin Polymerization with Chiral MetalloceneCatalysts”, Brintzinger, et al., Angew. Chem. Int. Ed. Engl., 1995, Vol.34, pp. 1143-1170, and the references therein; Bercaw et al., J. Am.Chem. Soc., 1999, Vol. 121, 564-573; and Bercaw et al., J. Am. Chem.Soc., 1996, Vol. 118, 11988-11989; each of which is incorporated hereinby reference.

In the practice of high throughput methods or combinatorial materialsscience, introduction of diversity may be important in designinglibraries or arrays. The synthetic schemes discussed herein will allowthose of skill in the art to introduce diversity on the ligands, whichmay assist in optimizing the selection of a particular ligand for aparticular polymerization reaction. Step 1 (see Schemel) may beconducted with, for example, any combination of the pyridines andanilines shown in Tables 1 and 2 (shown in FIGS. 1 and 2, respectively).The compounds shown in Tables 1 and 2 are meant to be illustrative andnon-limiting.

Compositions

Once the desired ligand is formed, it may be combined with a metal atom,ion, compound or other metal precursor compound. In some applications,the ligands of this invention will be combined with a metal compound orprecursor and the product of such combination is not determined, if aproduct forms. For example, the ligand may be added to a reaction vesselat the same time as the metal or metal precursor compound along with thereactants, activators, scavengers, etc. Additionally, the ligand can bemodified prior to addition to or after the addition of the metalprecursor, e.g. through a deprotonation reaction or some othermodification.

For formulas I, II, III, IV and V, the metal precursor compounds may becharacterized by the general formula Hf(L)_(n) where L is independentlyselected from the group consisting of halide (F, Cl, Br, I), alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl,substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl,aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy,aryloxy, hydroxy, boryl, silyl, amino, amine, hydrido, allyl, diene,seleno, phosphino, phosphine, carboxylates, thio, 1,3-dionates,oxalates, carbonates, nitrates, sulphates, ethers, thioethers andcombinations thereof; and optionally two or more L groups may be linkedtogether in a ring structure. n is 1, 2, 3, 4, 5, or 6. The hafniumprecursors may be monomeric, dimeric or higher orders thereof. It iswell known that hafnium metal typically contains some amount of impurityof zirconium. Thus, this invention uses as pure hafnium as iscommercially reasonable. Specific examples of suitable hafniumprecursors include, but are not limited to HfCl₄, Hf(CH₂Ph)₄,Hf(CH₂CMe₃)₄, Hf(CH₂SiMe₃)₄, Hf(CH₂Ph)₃Cl, Hf(CH₂CMe₃)₃Cl,Hf(CH₂SiMe₃)₃Cl, Hf(CH₂Ph)₂Cl₂, Hf(CH₂CMe₃)₂Cl₂, Hf(CH₂SiMe₃)₂Cl₂,Hf(NMe₂)₄, Hf(NEt₂)₄, and Hf(N(SiMe₃)₂)₂Cl₂. Lewis base adducts of theseexamples are also suitable as hafnium precursors, for example, ethers,amines, thioethers, phosphines and the like are suitable as Lewis bases.Specific examples include HfCl₄(THF)₂, HfCl₄(SMe₂)₂ andHf(CH₂Ph)₂Cl₂(OEt₂).

For formulas IV and V, the metal precursor compounds may becharacterized by the general formula M(L)_(n), where M is hafnium orzirconium and each L is independently selected from the group consistingof halide (F, Cl, Br, I), alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, substituted heteroalkyl,heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxy, aryloxy, hydroxy, boryl,silyl, amino, amine, hydrido, allyl, diene, seleno, phosphino,phosphine, carboxylates, thio, 1,3-dionates, oxalates, carbonates,nitrates, sulphates, ethers, thioethers and combinations thereof.Optionally two or more L groups may be linked together in a ringstructure. n is 4, typically. It is well known that hafnium metaltypically contains some amount of impurity of zirconium. Thus, thisinvention uses as pure hafnium or zirconium as is commerciallyreasonable. Specific examples of suitable hafnium and zirconiumprecursors include, but are not limited to HfCl₄, Hf(CH₂Ph)₄,Hf(CH₂CMe₃)₄, Hf(CH₂SiMe₃)₄, Hf(CH₂Ph)₃Cl, Hf(CH₂CMe₃)₃Cl,Hf(CH₂SiMe₃)₃Cl, Hf(CH₂Ph)₂Cl₂, Hf(CH₂CMe₃)₂Cl₂, Hf(CH₂SiMe₃)₂Cl₂,Hf(NMe₂)₄, Hf(NEt₂)₄, and Hf(N(SiMe₃)₂)₂Cl₂; ZrCl₄, Zr(CH₂Ph)₄,Zr(CH₂CMe₃)₄, Zr(CH₂SiMe₃)₄, Zr(CH₂Ph)₃Cl, Zr(CH₂CMe₃)₃Cl,Zr(CH₂SiMe₃)₃Cl, Zr(CH₂Ph)₂Cl₂, Zr(CH₂CMe₃)₂Cl₂, Zr(CH₂SiMe₃)₂Cl,Zr(NMe₂)₄, Zr(NEt₂)₄, Zr(NMe₂)₂Cl₂, Zr(NEt₂)₂Cl₂, and Zr(N(SiMe₃)₂)₂Cl₂.Lewis base adducts of these examples are also suitable as hafniumprecursors, for example, ethers, amines, thioethers, phosphines and thelike are suitable as Lewis bases. Specific examples include HfCl₄(THF)₂,HfCl₄(SMe₂)₂ and Hf(CH₂Ph)₂Cl₂(OEt₂).

The ligand to metal precursor compound ratio is typically in the rangeof about 0.01:1 to about 100:1, more preferably in the range of about0.1:1 to about 10:1.

Metal-Ligand Complexes

This invention, in part, relates to new metal-ligand complexes.Generally, the ligand is mixed with a suitable metal precursor compoundprior to or simultaneously with allowing the mixture to be contactedwith the reactants (e.g., monomers). When the ligand is mixed with themetal precursor compound, a metal-ligand complex may be formed, whichmay be a catalyst or may need to be activated to be a catalyst. Themetal-ligand complexes discussed herein are referred to as 2,1 complexesor 3,2 complexes, with the first number representing the number ofcoordinating atoms and second number representing the number of anionicsites on the ligand. The 2,1 complexes therefore have two coordinatingatoms and a single anionic charge. Other embodiments of this inventionare those complexes that have a general 3,2 coordination scheme to ametal center, with 3,2 referring to a ligand that occupies threecoordination sites on the metal and two of those sites being anionic andthe remaining site being a neutral Lewis base type coordination.

Looking first at the 2,1 metal-ligand complexes, the metal-ligandcomplexes may be characterized by the following general formula:

wherein T, J″, R¹, L and n are as defined previously; and x is 1 or 2.The J″ heteroaryl may or may not datively bond, but is drawn as bonding.More specifically, the metal-ligand complexes may be characterized bythe formula:

wherein R¹, T, R⁴, R⁵, R⁶, R⁷, L and n are as defined previously; and xis 1 or 2. In one preferred embodiment x=1 and n=3. Additionally, Lewisbase adducts of these metal-ligand complexes are also within the scopeof the invention, for example, ethers, amines, thioethers, phosphinesand the like are suitable as Lewis bases.

More specifically, the metal-ligand complexes of this invention may becharacterized by the general formula:

wherein the variables are generally defined above. Thus, e.g., Q², Q³,Q⁴, R², R³, R⁴, R⁵, R⁶ and R⁷ are independently selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, substituted heteroalkyl,heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl,phosphino, amino, thio, seleno, nitro, and combinations thereof;optionally, two or more R⁴, R⁵, R⁶, R⁷ groups may be joined to form afused ring system having from 3-50 non-hydrogen atoms in addition to thepyridine ring, e.g. generating a quinoline group; also, optionally, anycombination of R², R³ and R⁴ may be joined together in a ring structure;Q¹ and Q⁵ are selected from the group consisting of alkyl, substitutedalkyl, cycloalkyl, substituted cycloalkyl, aryl, substituted aryl,provided that Q¹ and Q⁵ are not both methyl; and each L is independentlyselected from the group consisting of halide, alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkylheterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxy, aryloxy, hydroxy, boryl,silyl, amino, amine, hydrido, allyl, diene, seleno, phosphino,phosphine, carboxylates, thio, 1,3-dionates, oxalates, carbonates,nitrates, sulphates, ethers, thioethers and combinations thereof; andoptionally two L groups may be linked together in a ring structure; n is1, 2, 3, 4, 5, or 6; and x=1 or 2.

In other embodiments, the 2,1 metal-ligand complexes can becharacterized by the general formula:

wherein the variables are generally defined above.

In still other embodiments, the 2,1 metal-ligand complexes of thisinvention can be characterized by the general formula:

wherein the variables are generally defined above. The more specificembodiments of the metal-ligand complexes of formulas VI, VII, VIII, IXand X are explained above with regard to the specifics described for theligands and metal precursors.

Lewis base adducts of these complexes are also suitable, for example,ethers, amines, thioethers, phosphines and the like are suitable asLewis bases (note the definition of L).

Turning to the 3,2 metal-ligand complexes of this invention, themetal-ligand complexes in this aspect of this invention may be generallycharacterized by the general formula:

where M is zirconium or hafnium;

R¹ and T are defined above;

J′″ being selected from the group of substituted heteroaryls with 2atoms bonded to the metal M, at least one of those 2 atoms being aheteroatom, and with one atom of J′″ is bonded to M via a dative bond,the other through a covalent bond; and L¹and L² are independentlyselected from the group consisting of halide, alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, heteroalkyl, substitutedheteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy,hydroxy, boryl, silyl, amino, amine, hydrido, allyl, diene, seleno,phosphino, phosphine, carboxylates, thio, 1,3-dionates, oxalates,carbonates, nitrates, sulphates, and combinations thereof; andoptionally the L groups may be linked together in a ring structure.

More specifically, the 3,2 metal-ligand complexes of this invention maybe characterized by the general formula:

where M is zirconium or hafnium;

T, R¹, R⁴, R⁵, R⁶, L¹and L² are defined above; and

E″ is either carbon or nitrogen and is part of an cyclic aryl,substituted aryl, heteroaryl, or substituted heteroaryl group.

Even more specifically, the 3,2 metal-ligand complexes of this inventionmay be characterized by the general formula:

where M is zirconium or hafnium; and

T, R¹, R⁴, R⁵, R⁶, R¹⁰, R¹¹,R¹², R¹³, L¹ and L² are defined above.

Still even more specifically, the 3,2 metal-ligand complexes of thisinvention may be characterized by the general formula:

where M is zirconium or hafnium; and

T, R¹, R⁴, R⁵, R⁶, R¹⁰, R¹¹, R¹², R¹³, Q¹, Q², Q³, Q⁴, Q⁵, L¹ and L² aredefined above.

The more specific embodiments of the metal-ligand complexes of formulasXI, XII, XIII and XIV are explained above with regard to the specificsdescribed for the ligands and metal precursors. Lewis base adducts ofthese complexes are also suitable, for example, ethers, amines,thioethers, phosphines and the like are suitable as Lewis bases.

In addition, preferences for the substituents on the ligands forproduction of the particular polymers discussed above (e.g., isotacticpolypropylene) apply to the metal-ligand complexes just described. Forisotactic polypropylene it is currently preferred that M is hafnium,although this preference is only slight as compared to zirconium. By“slight” here, it is meant that zirconium metal based polymerization ofpropylene for isotactic polypropylene shows similar tacticity control ascompared to hafnium metal based polymerization, however, the hafniumbased catalysts tend to show better polymerization activity andperformance overall.

For isotactic polypropylene production, it is currently preferred thatL¹and L² are the same and selected from the group consisting of alkyland dialkyl amino, more specifically from the group consisting of methyland dimethylamino.

As above, for production of isotactic polypropylene, R² and R³ are notthe same group, leading to a chiral center on the carbon atom from whichR² and R³ stem. In more specific embodiments, R² is hydrogen. In morespecific embodiments for isotactic polypropylene production R³ isselected from the group consisting of hydrogen, halide, alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl,substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl,aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy,aryloxy, silyl, boryl, phosphino, amino, thio, seleno, nitro, andcombinations thereof. In more specific embodiments for isotacticpolypropylene production R³ is aryl, substituted aryl, heteroaryl orsubstituted heteroaryl. In more specific embodiments for isotacticpolypropylene production R³ is selected from the group consisting ofbenzyl, phenyl, 2-biphenyl, 2-dimethylaminophenyl, 2-methoxyphenyl,anthracenyl, mesityl, 2-pyridyl, 3,5-dimethylphenyl, o-tolyl andphenanthrenyl.

In the above formulas, R¹⁰, R¹¹, R¹² and R¹³ are independently selectedfrom the group consisting of hydrogen, halide, alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, heteroalkyl, substitutedheteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy,silyl, boryl, phosphino, amino, thio, seleno, nitro, and combinationsthereof; optionally, two or more R¹⁰, R¹¹, R¹² and R¹³ groups may bejoined to form a fused ring system having from 3-50 non-hydrogen atoms.Particular embodiments include, for example, for isotactic polypropyleneproduction, it is currently preferred that R¹⁰, R¹¹, R¹², R¹³, are eachhydrogen; or one or more of R¹⁰, R¹¹, R¹², R¹³ are methyl, fluoro,trifluoromethyl, methoxy, or dimethylamino; or where R¹⁰ and R¹¹ arejoined to form a benzene ring and R¹² and R¹³ are each hydrogen (thusforming a napthyl group with the existing phenyl ring).

Specific 2,1 and 3,2 metal complexes that are useful for the productionof isotactic polypropylene include:

For the production of ethylene-styrene copolymers, there are differentpreferences depending on the type of polymer that is desired. In someembodiments, it is preferred that the above formulas for complexes areused, particularly with R⁷ selected from the group consisting of aryl,substituted aryl, heteroaryl, and substituted heteroaryl. Specific 2,1and 3,2 complexes that are preferred for ethylene-styrene copolymerproduction include:

For the production of ethylene-1-octene copolymers, it is preferred thatthe metal complexes of the above general formulas are used, with eitheror both of R³ and/or R⁷ being independently selected from the groupconsisting of aryl, substituted aryl, heteroaryl, and substitutedheteroaryl. Specific 2,1 and 3,2 metal complexes that are preferred forethylene-1-octene copolymer production include:

In addition, Lewis base adducts of the metal-ligand complexes in theabove formulas are also suitable, for example, ethers, amines,thioethers, phosphines and the like are suitable as Lewis bases.

The metal-ligand complexes can be formed by techniques known to those ofskill in the art, such as combinations of metal precursors and ligandsunder conditions to afford complexation. In some embodiments, R¹⁴ ishydrogen and the metal-ligand complexes are formed by a metallationreaction (in situ or not) as shown below in scheme 3:

In scheme 3, R¹⁴ is hydrogen (but see above for the full definition ofR¹⁴ in other embodiments of this invention). The metallation reaction toconvert the 2,1 complex on the left to the 3,2 complex on the right canoccur via a number of mechanisms, likely depending on the substituentschosen for L¹, L² and L³ and the other substituents such as Q¹-Q⁵,R²-R⁶, R¹⁰ to R¹³. In one embodiment, when L¹, L² and L³ are eachN(CH₃)₂, the reaction can proceed by heating the 2,1 complex to atemperature above about 100° C. In this embodiment, it is believed thatL¹ and L² remain N(CH₃)₂ in the 3,2 complex. In another embodiment whenL¹, L² and L³ are each N(CH₃)₂, the reaction can proceed by adding agroup 13 reagent (as described below) to the 2,1 complex at a suitabletemperature (such as room temperature). Preferably the group 13 reagentfor this purpose is di-isobutyl aluminum hydride, tri-isobutyl aluminumor trimethyl aluminum. In this embodiment, L¹and L² are typicallyconverted to the ligand (e.g., alkyl or hydride) stemming from the group13 reagent (e.g., from trimethyl aluminum, L¹ and L² are each CH₃ in the3,2 complex). The 2,1 complex in scheme 3 is formed by the methodsdiscussed above.

In an alternative embodiment possibly outside the scope of scheme 3, forisotactic polypropylene production, it is currently preferred that R¹⁴is either hydrogen or methyl.

Various references disclose metal complexes that may appear to besimilar; see for example, U.S. Pat. Nos. 6,103,657 and 5,637,660, bothof which are incorporated herein by reference for all purposes. However,certain embodiments of the invention herein provide unexpectedlyimproved polymerization performance (e.g., higher activity and/or higherpolymerization temperatures and/or higher comonomer incorporation)relative to the embodiments disclosed in those references. Inparticular, as shown in certain of the examples herein, the activity ofthe hafnium metal catalysts is far superior to that of the zirconiumcatalysts. Indeed, it also appears as if the zirconium metal centeredcatalysts have inferior performance with respect to incorporation ofcomonomer into an ethylene/comonomer type copolymer, especially for1-octene, isobutylene and styrene comonomers.

The ligands, complexes or catalysts may be supported on an organic orinorganic support. Suitable supports include silicas, aluminas, clays,zeolites, magnesium chloride, polyethyleneglycols, polystyrenes,polyesters, polyamides, peptides and the like. Polymeric supports may becross-linked or not. Similarly, the ligands, complexes or catalysts maybe supported on similar supports known to those of skill in the art. Inaddition, the catalysts of this invention may be combined with othercatalysts in a single reactor and/or employed in a series of reactors(parallel or serial) in order to form blends of polymer products.

Polymerization Activators/Additives

The metal-ligand complexes and compositions are active catalyststypically in combination with a suitable activator, combination ofactivators, activating technique or activating package, although some ofthe ligand-metal complexes may be active without an activator oractivating technique. Broadly, the activator(s) may comprise alumoxanes,Lewis acids, Bronsted acids, compatible non-interfering activators andcombinations of the foregoing. These types of activators have beentaught for use with different compositions or metal complexes in thefollowing references, which are hereby incorporated by reference intheir entirety: U.S. Pat. Nos. 5,599,761, 5,616,664, 5,453,410,5,153,157, 5,064,802, and EP-A-277,004. In particular, ionic or ionforming activators are preferred.

Suitable ion forming compounds useful as an activator in one embodimentof the present invention comprise a cation that is a Bronsted acidcapable of donating a proton, and an inert, compatible, non-interfering,anion, A⁻. Preferred anions are those containing a single coordinationcomplex comprising a charge-bearing metal or metalloid core.Mechanistically, said anion should be sufficiently labile to bedisplaced by olefinic, diolefinic and unsaturated compounds or otherneutral Lewis bases such as ethers or nitrites. Suitable metals include,but are not limited to, aluminum, gold and platinum. Suitable metalloidsinclude, but are not limited to, boron, phosphorus, and silicon.Compounds containing anions that comprise coordination complexescontaining a single metal or metalloid atom are, of course, well knownand many, particularly such compounds containing a single boron atom inthe anion portion, are available commercially.

Preferably such activators may be represented by the following generalformula:

(L*—H)_(d) ⁺(A^(d−))

wherein, L* is a neutral Lewis; (L*—H)⁺ is a Bronsted acid; A^(d−) is anon-interfering, compatible anion having a charge of d−, and d is aninteger from 1 to 3. More preferably A^(d−) corresponds to the formula:[M′³⁺Q_(h)]^(d−) wherein h is an integer from 4 to 6; h−3=d; M′ is anelement selected from Group 13 of the Periodic Table of the Elements;and Q is independently selected from the group consisting of hydride,dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, andsubstituted-hydrocarbyl radicals (including halidesubstitutedhydrocarbyl, such as perhalogenated hydrocarbyl radicals), said Q havingup to 20 carbons. In a more preferred embodiment, d is one, i.e., thecounter ion has a single negative charge and corresponds to the formulaA⁻.

Activators comprising boron or aluminum which are particularly useful inthe preparation of catalysts of this invention may be represented by thefollowing general formula:

[L*—H]⁺[JQ₄]⁻

wherein: L* is as previously defined; J is boron or aluminum; and Q is afluorinated C₁₋₂₀ hydrocarbyl group. Most preferably, Q is independentlyselected from the group selected from the group consisting offluorinated aryl group, especially, a pentafluorophenyl group (i.e., aC₆F₅ group) or a 3,5-bis(CF₃)₂C₆H₃ group. Illustrative, but notlimiting, examples of boron compounds which may be used as an activatingcocatalyst in the preparation of the improved catalysts of thisinvention are tri-substituted ammonium salts such as: trimethylammoniumtetraphenylborate, triethylammonium tetraphenylborate, tripropylammoniumtetraphenylborate, tri(n-butyl)ammonium tetraphenylborate,tri(t-butyl)ammonium tetraphenylborate, N,N-dimethylaniliniumtetraphenylborate, N,N-diethylanilinium tetraphenylborate,N,N-dimethylanilinium tetra-(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium) tetraphenylborate,trimethylammonium tetrakis(pentafluorophenyl) borate, triethylammoniumtetrakis(pentafluorophenyl) borate, tripropylammoniumtetrakis(pentafluorophenyl) borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl) borate, tri(secbutyl)ammoniumtetrakis(pentafluorophenyl) borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl) borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl) borate,N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis(pentafluorophenyl)borate, trimethylammonium tetrakis-(2,3,4,6-tetrafluorophenylborate andN,N-dimethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl) borate;dialkyl ammonium salts such as: di-(i-propyl)ammoniumtetrakis(pentafluorophenyl) borate, and dicyclohexylammoniumtetrakis(pentafluorophenyl) borate; and tri-substituted phosphoniumsalts such as: triphenylphosphonium tetrakis(pentafluorophenyl) borate,tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl) borate, andtri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl) borate;and N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate. Preferred [L*—H]⁺cations are N,N-dimethylanilinium and tributylammonium. Preferred anionsare tetrakis(3,5-bis(trifluoromethyl)phenyl)borate andtetrakis(pentafluorophenyl)borate. In some embodiments, the mostpreferred activator is PhNMe₂H+B(C₆F₅)₄ ⁻.

Other suitable ion forming activators comprise a salt of a cationicoxidizing agent and a non-interfering, compatible anion represented bythe formula:

(OX^(e+))_(d)(A^(d−))_(e)

wherein: Ox^(e+) is a cationic oxidizing agent having a charge of e+; eis an integer from 1to 3; and A^(d−), and d are as previously defined.Examples of cationic oxidizing agents include: ferrocenium,hydrocarbyl-substituted ferrocenium, Ag⁺, or Pb⁺². Preferred embodimentsof A^(d−) are those anions previously defined with respect to theBronsted acid containing activating cocatalysts, especiallytetrakis(pentafluorophenyl)borate.

Another suitable ion forming, activating cocatalyst comprises a compoundthat is a salt of a carbenium ion or silyl cation and a non-interfering,compatible anion represented by the formula:

{circle around (C)}⁺A⁻

wherein: {circle around (C)}⁺ is a C₁₋₁₀₀ carbenium ion or silyl cation;and A⁻ is as previously defined. A preferred carbenium ion is the tritylcation, i.e. triphenylcarbenium. The silyl cation may be characterizedby the formula Z¹Z²Z³Si⁺ cation, where each of Z¹, Z², and Z³ isindependently selected from the group consisting of alkyl, substitutedalkyl, cycloalkyl, heterocycloalkyl, heterocyclic, aryl, substitutedaryl, heteroaryl, substituted heteroaryl and combinations thereof. Insome embodiments, a most preferred activator is Ph₃C⁺B(C₆F₅)₄ ⁻.

Other suitable activating cocatalysts comprise a compound that is asalt, which is represented by the formula (A*^(+a))_(b)(Z*J*_(j))^(−c)_(d) wherein A* is a cation of charge +a; Z* is an anion group of from1to 50, preferably 1 to 30 atoms, not counting hydrogen atoms, furthercontaining two or more Lewis base sites; J* independently eachoccurrence is a Lewis acid coordinated to at least one Lewis base siteof Z*, and optionally two or more such J* groups may be joined togetherin a moiety having multiple Lewis acidic functionality; j is a numberform 2 to 12; and a, b, c, and d are integers from 1to 3, with theproviso that a×b is equal to c×d. See, WO 99/42467, which isincorporated herein by reference. In other embodiments, the anionportion of these activating cocatalysts may be characterized by theformula ((C₆F₅)₃M″″—LN—M″″(C₆F₅)₃)⁻ where M″″ is boron or aluminum andLN is a linking group, which is preferably selected from the groupconsisting of cyanide, azide, dicyanamide and imidazolide. The cationportion is preferably a quaternary amine. See, e.g., LaPointe, et al.,J. Am. Chem. Soc. 2000, 122, 9560-956 1, which is incorporated herein byreference.

In addition, suitable activators include Lewis acids, such as thoseselected from the group consisting of tris(aryl)boranes,tris(substituted aryl)boranes, tris(aryl)alanes, tris(substitutedaryl)alanes, including activators such as tris(pentafluorophenyl)borane.

Other useful ion forming Lewis acids include those having two or moreLewis acidic sites, such as those described in WO 99/06413 or Piers, etal. “New Bifunctional Perfluoroaryl Boranes: Synthesis and Reactivity ofthe ortho-Phenylene-Bridged Diboranes 1,2-[B(C₆F₅)₂]₂C₆X4(X=H, F)”, J.Am. Chem. Soc., 1999, 121, 3244-3245, both of which are incorporatedherein by reference. Other useful Lewis acids will be evident to thoseof skill in the art. In general, the group of Lewis acid activators iswithin the group of ion forming activators (although exceptions to thisgeneral rule can be found) and the group tends to exclude the group 13reagents listed below. Combinations of ion forming activators may beused.

Other general activators or compounds useful in a polymerizationreaction may be used. These compounds may be activators in somecontexts, but may also serve other functions in the polymerizationsystem, such as alkylating a metal center or scavenging impurities.These compounds are within the general definition of “activator,” butare not considered herein to be ion-forming activators. These compoundsinclude a group 13 reagent that may be characterized by the formulaG¹³R′_(3−p)D_(p) where G¹³ is selected from the group consisting of B,Al, Ga, In and combinations thereof, p is 0, 1 or 2, each R′ isindependently selected from the group consisting of alkyl, substitutedalkyl, cycloalkyl, heterocycloalkyl, heterocyclic and combinationsthereof, and each D is independently selected from the group consistingof halide, hydride, alkoxy, aryloxy, amino, thio, phosphino andcombinations thereof. In other embodiments, the group 13 activator is anoligomeric or polymeric alumoxane compound, such as methylalumoxane andthe known modifications thereof. In other embodiments, a divalent metalreagent may be used that is defined by the general formulaM′R′_(2−p)D_(p) and p′ is 0 or 1in this embodiment and R′ and D are asdefined above. M′ is the metal and is selected from the group consistingof Mg, Ca, Sr, Ba, Zn, Cd and combinations thereof. In still otherembodiments, an alkali metal reagent may be used that is defined by thegeneral formula M″R′ and in this embodiment R¹ is as defined above. M″is the alkali metal and is selected from the group consisting of Li, Na,K, Rb, Cs and combinations thereof. Additionally, hydrogen and/orsilanes may be used in the catalytic composition or added to thepolymerization system. Silanes may be characterized by the formulaSiR′_(4−q)D_(q) where R′ is defined as above, q is 1, 2, 3 or 4 and D isas defined above, with the proviso that there is at least one D that isa hydride.

The molar ratio of metal:activator (whether a composition or complex isemployed as a catalyst) employed preferably ranges from 1:10,000 to100:1, more preferably from 1:5000 to 10:1, most preferably from 1:10 to1:1. In a preferred embodiment of the invention mixtures of the abovecompounds are used, particularly a combination of a group 13 reagent andan ion-forming activator. The molar ratio of group 13 reagent toion-forming activator is preferably from 1:10,000 to 1000:1, morepreferably from 1:5000 to 100:1, most preferably from 1:100 to 100:1. Ina preferred embodiment, the ion forming activators are combined with atri-alkyl aluminum, specifically trimethylaluminum, triethylaluminum,tri-n-octylaluminum, or triisobutylaluminum or with a di-alkyl aluminumhydride such as di-isobutyl aluminum hydride. A most preferredcombination is about 1 equivalent of N,N-dimethylaniliniumtetrakis(pentafluorophenyl) borate, and 5-30 equivalents of a Group 13reagent. For ethylene-isobutylene copolymerization the group 13 reagentshould be present in at least an amount that is 0.1 equivalents of themetal (e.g., the metal presecur compound) and preferably in an amountthat is between 1 and 10 equivalents of the metal.

In other applications, the ligand will be mixed with a suitable metalprecursor compound prior to or simultaneous with allowing the mixture tobe contacted to the reactants. When the ligand is mixed with the metalprecursor compound, a metal-ligand complex may be formed, which may be acatalyst. In connection with the metal-ligand complex and depending onthe ligand or ligands chosen, the metal-ligand complex may take the formof dimers, trimers or higher orders thereof or there may be two or moremetal atoms that are bridged by one or more ligands. Furthermore, two ormore ligands may coordinate with a single metal atom. The exact natureof the metal-ligand complex(es) or compound(s) formed depends on thechemistry of the ligand and the method of combining the metal precursorand ligand, such that a distribution of metal-ligand complexes may formwith the number of ligands bound to the metal being greater or less thanthe number of equivalents of ligands added relative to an equivalent ofmetal precursor.

Monomers/Polymers

The compositions, complexes and/or catalysts of this invention areparticularly effective at polymerizing α-olefins (such as propylene,1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and styrene),copolymerizing ethylene with α-olefins (such as propylene, 1-butene,1-pentene, 1-hexene, 1-heptene, 1-octene, and styrene), andcopolymerizing ethylene with 1,1-disubstituted olefins (such asisobutylene). These compositions might also polymerize monomers thathave polar functionalities in homopolymerizations or copolymerizationsand/or homopolymerize 1,1-disubstituted olefins. Also, diolefins incombination with ethylene and/or α-olefins or 1,1-disubstituted olefinsmay be copolymerized. The new catalyst compositions can be prepared bycombining a metal precursor with a suitable ligand and, optionally, anactivator or combination of activators.

In general monomers useful herein may be olefinically or unsaturatedmonomers having from 2 to 20 carbon atoms either alone or incombination. Generally, monomers may include olefins, diolefins andunsaturated monomers including ethylene and C₃ to C₂₀ □α-olefin such aspropylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene,1-norbornene, styrene and mixtures thereof; additionally,1,1-disubstituted olefins, such as isobutylene, 2-methyl-1-butene,2-methyl-1-pentene, 2-ethyl-1-pentene, 2-methyl-1-hexene,3-trimethylsilyl-2-methyl-1-propene, α-methyl-styrene, either alone orwith other monomers such as ethylene or C₃ to C₂₀ α-olefins and/ordiolefins. The α-olefins listed above may be polymerized in astereospecific manner e.g. to generate isotactic or syndiotactic orhemiisotactic polypropylene. Additionally the α-olefins may bepolymerized to produce a polymer with differing tacticity sequenceswithin the polymer chain, such as polypropylene containing atactic andisotactic sequences within the same polymer chain. These definitions areintended to include cyclic olefins. Diolefins generally comprise1,3-dienes such as (butadiene), substituted 1,3-dienes (such asisoprene) and other substituted 1,3-dienes, with the term substitutedreferring to the same types of substituents referred to above in thedefinition section. Diolefins also comprises 1,5-dienes and othernon-conjugated dienes. The styrene monomers may be unsubstituted orsubstituted at one or more positions on the aryl ring. The use ofdiolefins in this invention is typically in conjunction with anothermonomer that is not a diolefin. In some embodiments, acetylenicallyunsaturated monomers may be employed.

More specifically, it has been found that the catalysts of the presentinvention are particularly active for certain monomers, particularlyα-olefins. Thus, the catalysts of the present invention may providehigher comonomer incorporation for copolymers of ethylene andco-monomers having three or more carbon atoms.

In addition, the catalysts of the present invention may polymerize vinylchloride alone (e.g., in a homopolymerization) or with other monomers(such as ethylene or C₃ to C₂₀ α-olefins). Furthermore, vinyl monomerswith functional groups may also be polymerized alone (e.g., in ahomopolymerization) or with other monomers (such as ethylene or C₃ toC₂₀ α-olefins). Such functional group containing vinyl monomers can becharacterized by the general formula H₂C═CH—FG, where FG is thefunctional group that contains at least one heteroatom (using theprevious definition) or halogen (e.g., Cl, F, Br, etc.). Functionalmonomers include C₁-C₂₀ acrylates, C₁-C₂₀ methacrylates, C₁-C₂₀vinylacetates, acrylic acid, methacrylic acid, maleic anhydride, vinylacetate, vinyl ethers, acrylonitrile, acrylamide, vinyl chloride andmixtures thereof.

Novel polymers, copolymers or interpolymers may be formed having uniquephysical and/or melt flow properties. Such novel polymers can beemployed alone or with other polymers in a blend to form products thatmay be molded, cast, extruded or spun. End uses for the polymers madewith the catalysts of this invention include films for packaging, trashbags, bottles, containers, foams, coatings, insulating devices andhousehold items. Also, such functionalized polymers are useful as solidsupports for organometallic or chemical synthesis processes.

More specifically, the catalysts of this invention have prepared novelcopolymers of ethylene and isobutylene. These novel polymers have highmolecular weight combined with high incorporation of isobutylene. Othershave broadly claimed such copolymers. See e.g., U.S. Pat. Nos. 5,866,665and 5,763,556, which are both incorporated herein by reference. However,the combination of these properties has not been previously exemplifiedand is commercially promising. More specifically, the novel copolymershave a number average molecular weight of at least 50,000 and a weightpercent incorporation of isobutylene of at least about 30 wt. %.

Also, it has been found that the catalytic performance at hightemperature of particular catalysts of the present invention for thepolymerization of olefins in general, including the co-polymerization ofethylene and α-olefins, is unexpectedly good. In particular, it has beenfound that varying the ligand substituents (R and Q groups) discussedherein allows one to increase the polymerization performance and polymermolecular weight for olefin polymerizations at high temperatures,particularly for polymerization temperatures above 120° C. Inparticular, when R³ is aryl or substituted aryl, the high temperaturepolymerization catalytic performance is improved compared to when R³ ishydrogen or alkyl. Also, the steric bulk of the R¹ and R⁷ groups canaffect polymeization performance. In particular, improved hightemperature polymerization performance is observed when Q¹and Q⁵ areboth not hydrogen.

It has been found that particular catalysts of the present inventionco-polymerize ethylene and styrene (or substituted styrenes), formingethylene-styrene copolymers. In particular, it has been found thatvarying the ligand substituents (R and Q groups) discussed herein allowsone to vary the ratio of styrene to ethylene incorporated in thecopolymer, and the ethylene-styrene copolymerization activity and Mw ofthe resulting ethylene-styrene copolymer. In particular, when R⁷ is arylor substituted aryl, the ratio of styrene to ethylene incorporated inthe copolymer is significantly higher than when R⁷ is hydrogen or alkyl.The higher level of styrene incorporation when R⁷ is aryl or substitutedaryl is unexpected.

The α-olefins listed above may be polymerized in a stereospecific mannere.g. to generate isotactic or syndiotactic or hemiisotacticpoly-α-olefins. Additionally the α-olefins may be polymerized to producea polymer with differing tacticity sequences within the polymer chain,such as polypropylene containing atactic and isotactic sequences withinthe same polymer chain. The stereoregularity may be interrupted bystereoerrors, in particular isolated stereoerrors have been observed,which is an indication of enantiomorphic side control. Also regioerrorsmight be present in the isotactic polypropylene polymer as it isdescribed in the literature. In particular isolated 2-1 insertions maybe observed. (see, e.g., Resconi et al., “Selectivity in PropenePolymerization with Metallocene Catalysts,” Chem. Rev. 2000, 100,1253-1345).

More specifically, it has been found that particular catalysts of thepresent invention polymerize propylene to isotactic or crystallinepolypropylene, forming polymers with novel properties. Thispolymerization activity for isotactic polypropylene has surprisingperformance in a solution process. In particular, it has been found thatvarying the R and Q groups discussed herein allows one to vary thecrystallinity index of the crystalline polypropylene formed. In general,reducing the steric bulk of the R¹ group results in a polymer having alower crystallinity index, such that when Q¹ and Q⁵ are both methyl,tacticity may be insufficient to provide a crystalline polymer. Also,the steric bulk of the R³ and R⁷ group can affect the crystallinityindex.

The isotactic polypropylene polymers formed from these catalysts in asolution polymerization process have a crystallinity index of betweenabout 0.35 and about 0.95, more specifically between about 0.65 and 0.95and in some embodiments preferably above about 0.8, under thepolymerization conditions employed. The crystallinity index isdetermined using FTIR as is known to those of skill in the art andcalibrated based on a relative scale. In one embodiment, thecrystallinity index value can be determined using commercially availableFTIR equipment (such as a Bruker Equinox 55 with an IR Scope II inreflection mode using Pike MappIR software). The crystallinity index isobtained from the ratio of band heights at 995 cm⁻¹ and 972 cm⁻¹.Atactic polypropylene has a ratio of band heights or crystallinity indexof 0.2. Greater than 98% isotactic polypropylene has a crystallinityindex ratio of greater than 0.95. Generally, the amount of error incrystallinity index measurements is ±10.05. Polymer blends of variouscompositions show a linear relationship between % isotacticity andcrystallinity index. See, for example, J. P. Luongo, J. Appl. Polym.Sci., 3 (1960) 302-309 and T. Sundell, H. Fagerholm, H. Crozier, Polymer37 (1996) 3227-3231, each of which is incorporated herein by reference.

As those of skill in the art will recognize, isotacticity can also berepresented by percent pentads (%mmmm) as determined by ¹³C NMRspectroscopy. Proton decoupled ¹³C NMR spectroscopy can be performedusing commercially available equipment (such as a Bruker 300 MHz at 100°C. probe temperature) to determine the degree of tacticity as %mmmmpentads (for assignment of ¹³C signals see the review Brintzinger H. H.et al., Angew. Chem. Int. Ed. Eng. 1995, 34, 1143, which is incorporatedherein by reference). For example, a 15-30 mg polymer sample isdissolved in a 1:1 mixture of C₂D₂Cl₄ and C₂Cl₄ by heating the sample toca. 100° C. The %mmmm is determined by the ratio of peak integral from23.5 to 21.5 ppm and peak integral 23.5 to 19 ppm. Proton decoupled ¹³CNMR spectroscopy can be also performed to determine the frequency of andnature of stereoerrors and regioerrors.

In addition, the melting point of the crystalline polypropylene isgenerally in the range of from about 115° C. to about 160° C., morespecifically between about 120° C. and 155° C., and in some embodimentspreferably above about 135° C. Melting points are determined bydifferential scanning calorimetry, as is known in the art (see also theexample section, herein). Surprisingly, the tacticity level and meltingpoint are relatively level throughout different polymerizationtemperatures.

The weight average molecular weight of the crystalline polypropyleneaccording to this application ranges from about 15,000 to about4,500,000 and for some embodiments more specifically between about50,000 to about 500,000 for the polymerization condition of apolymerization temperature at or above about 110° C. The polydispersityof the crystalline polypropylene of this invention (M_(w)/M_(n)) isgenerally about 2.5 or lower and in alternative embodiments is betweenabout 2.0 and 3.5. Molecular weight and polydispersity index isdetermined according to method known to those of skill in the art,based, generally on polystyrene standards. As those of skill in the artwill recognize, error in molecular weight measurements can range from10-20%.

Novel polymers, copolymers or interpolymers may be formed having uniquephysical and/or melt flow properties. Polymers that can be preparedaccording to the present invention include propylene copolymers with atleast one C₄-C₂₀ α-olefin, particularly 1-butene, 1-hexene,4-methyl-1-pentene and 1-octene. The copolymers of propylene with atleast one C₄-C₂₀ α-olefin comprise from about 0.1 wt. % higher olefin toabout 60 wt. % higher olefin, more specifically from about 0.2 wt. %higher olefin to about 50 wt. % higher olefin and still morespecifically from about 2 wt. % higher olefin to about 30 wt. % higherolefin. For certain embodiments of this invention, crystallinecopolymers include those of propylene and a comonomer selected from thegroup consisting of ethylene, 1-butene, 1-hexene, and 1-octene comprisefrom about 0.2 to about 30 wt. % comonomer, more specifically from about1 to about 20 wt. % comonomer, even more specifically from about 2 toabout 15 wt. % comonomer and most specifically from about 5 to about 12wt. % comonomer.

The novel polymers (such as isotactic polypropylene) disclosed hereincan be employed alone or with other natural or synthetic polymers in ablend. Such other natural or synthetic polymers can be polyethylene(including linear low density polyethylene, low density polyethylene,high density polyethylene, etc.), atactic polypropylene, nylon, EPDM,ethylene-propylene elastomer copolymers, polystyrene (includingsyndiotactic polystryene), ethylene-styrene copolymers and terpolymersof ethylene-styrene and other C₃-C₂₀ olefins (such as propylene).

Melt flow rate (MRF) for polypropylene and copolymer of propylene andone or more C₄-C₂₀ α-olefins is measured according to ASTM D-1238,condition L (2.16 kg, 230° C.). In some embodiments of this invention,the MFR is in the range of 0.005-1,000, more specifically 0.01-500 andeven more specifically 0.1-100. Flex modulus for polypropylene andcopolymer of propylene and one or more C₄-C₂₀ α-olefins is measuredaccording to ASTM D-790. In some embodiments of this invention, the flexmodulus ranges from 20,000-400,000 psi, more specifically from20,000-300,000 psi and even more specifically from 100,000-200,000 psi.Notch izod impact for polypropylene and copolymer of propylene and oneor more C₄-C₂₀ α-olefins is measured according to ASTM D-256A. In someembodiments of this invention, the notch izod impact ranges from 0.1 tono break in ft-lbs/in.

The novel polypropylene and copolymer of propylene and one or moreC₄-C₂₀ α-olefins disclosed in the present invention are useful for awide variety of applications, including films (such as blown and castfilm, clarity film and multi-layer films), thermoforming (such as cups,plates, trays and containers), injection moulding, blow-moulding, foams(such as structural foams), pipe (such as potable water pipe and highpressure pipe), automotive parts, and other applications that will beevident to those of skill in the art.

Melt strength (measured in cN) and melt drawability (measured in mm/s)tests are conducted by pulling (“taking-up”) strands of the moltenpolymers or blends at constant acceleration until breakage occurs. Anexperimental set-up comprises a capillary rheometer and a Rheotensapparatus as a take-up device. The molten strands are drawn uniaxiallyto a set of accelerating nips located 100 mm below the die. The forcerequired to uniaxially extend the strands is recorded as a function ofthe take-up velocity or the nip rolls. In the case of polymer meltsexhibiting draw resonance (indicated by the onset of a periodicoscillation of increasing amplitude in the measured force profile), themaximum force and wheel velocity before the onset of draw resonance aretaken as the melt strength and melt drawability, respectively. In theabsence of draw resonance, the maximum force attained during testing isdefined as the melt strength and the velocity at which breakage occursis defined as the melt drawability. These tests are typically run underthe following conditions:

Mass flow rate 1.35 grams/min Temperature 190° C. Equilibration time at190° C. 10 minutes Die 20:1 (with entrance angle of approximately 45degrees) Capillary length 41.9 mm Capillary diameter 2.1 mm Pistondiameter 9.54 mm Piston velocity 0.423 mm/s Shear rate 33.0 s⁻¹Draw-down distance (die 100 mm exit to take-up sheels) Coolingconditions Ambient air Acceleration 2.4 mm/s²

For some aspects of the present invention the novel polymers are usefulto produce foams having improved properties. For foams and otherapplications requiring melt strength, the MFR is typically in the rangeof 0.1-10, more specifically in the range of 0.3-3 and most specificallyin the range of 0.5-2. The melt strength is typically greater than 5 cN,more specifically greater than 9 cN and most specifically greater than12 cN.

The drawability is typically greater than 15 mm/sec, more specificallygreater than 25 mm/sec and most specifically greater than 35 mm/sec.

In some aspects of the present invention, the novel polymers disclosedherein are useful for a wide variety of applications where certainoptical properties are beneficial. Gloss is measured according to ASTMD-1746. Haze is measured according to ASTM D-1003 and clarity ismeasured according to ASTM D-2457. The novel polymers disclosed hereinin some aspects are films having haze of less than 10%. In additionfilms having clarity of greater than 91% may be beneficially obtained.

Polymerization Systems

Polymerization can be carried out in the Ziegler-Natta or Kaminsky-Sinnmethodology, including temperatures of from −100° C. to 300° C. andpressures from atmospheric to 3000 atmospheres. Suspension, solution,slurry, gas phase or high-pressure polymerization processes may beemployed with the catalysts and compounds of this invention. Suchprocesses can be run in a batch, semi-batch or continuous mode. Examplesof such processes are well known in the art. A support for the catalystmay be employed, which may be inorganic (such as alumina, magnesiumchloride or silica) or organic (such as a polymer or cross-linkedpolymer). Methods for the preparation of supported catalysts are knownin the art. Slurry, suspension, gas phase and high-pressure processes asknown to those skilled in the art may also be used with supportedcatalysts of the invention.

Other additives that are useful in a polymerization reaction may beemployed, such as scavengers, promoters, modifiers and/or chain transferagents, such as hydrogen, aluminum alkyls and/or silanes.

As discussed herein, catalytic performance can be determined a number ofdifferent ways, as those of skill in the art will appreciate. Catalyticperformance can be determined by the yield of polymer obtained per moleof metal complex, which in some contexts may be considered to beactivity. Table 3 (FIG. 3) and Table 4 (FIG. 4) display the results ofethylene-1-octene copolymerizations using ancillary ligands of theinvention in combination with hafnium and zirconium precursors,respectively. In the case of zirconium, Table 4 illustrates that theyield of copolymer obtained from the experiments is the highest when thezirconium precursor (Zr(CH₂C₆H₅)₄) is employed without the use of anancillary ligand (Table 4 in FIG. 4; Cell A3: 369 mg). This illustratesthat the presence of the ancillary ligand may not necessarily enhancethe catalytic activity of the zirconium metal center. In the case ofhafnium, the yields are unexpected high. In contrast to zirconium, theyield of copolymer obtained when the hafnium precursor (Hf(CH₂C₆H₅)₄) isemployed without the use of an ancillary ligand is very low (Table 3 inFIG. 3; Cell A3: 47 mg).

Another measure of catalyst polymerization performance is co-monomerincorporation. As is well known in the art, many ethylene copolymers areprepared using ethylene and at least one other monomer. These copolymersor higher order polymers in some applications require higher amounts ofadditional co-monomer(s) than have been practical with known catalysts.Since ethylene tends to be the most reactive monomer, obtaining higherco-monomer incorporations is a benefit that is examined forpolymerization catalysts. Two useful co-monomers are 1-octene andstyrene. This invention offers the possibility of higher incorporationof co-monomers such as 1-octene and styrene. As shown herein, theethylene/l-octene copolymers obtained from the combination of ancillaryligands and zirconium precursors all possess lower weight % 1-octenevalues (<11 wt. %) (Table 4 in FIG. 4), than the weight % 1-octenevalues for the ethylene/1-octene copolymers obtained from thecombination of ancillary ligands and hafnium precursors.

The results of the ethylene-1-octene copolymerizations using ancillaryligands of the invention in combination with a hafnium metal precursorare surprising (Table 3 in FIG. 3). In contrast to zirconium, the yieldof copolymer obtained when the hafnium precursor (Hf(CH₂C₆H₅)₄) isemployed without the use of an ancillary ligand is very low (cell A3: 47mg). Surprisingly, in the presence of certain ancillary ligands, theyields of copolymers obtained are enhanced dramatically relative to cellA3. In addition, the copolymers obtained typically possess higher wt. %1-octene values relative to the values shown in Table 4. Additionallythe wt. % 1-octene values for the copolymers obtained span a wider range(<10 wt. % to 23 wt. %). In contrast to Table 4, the results in Table 3illustrate the ability of the ancillary ligand to tailor the catalyticperformance of the hafnium metal center, both in terms of catalyticactivity and the ability to incorporate 1-octene.

Tables 5 and 5a display the results of ethylene-styrenecopolymerizations using ancillary ligands of the invention incombination with hafnium and zirconium precursors. The results in Tables5 and 5 a illustrate that certain combinations of ancillary ligands withhafnium precursors are more productive in the copolymerization ofethylene with styrene than are combinations of the same ancillaryligands with zirconium precursors. Additionally the results illustratecombinations of ancillary ligands with hafnium precursors to producecopolymers with a higher styrene incorporation (wt % styrene by NMR inTable 5 and mol % styrene by FTIR in Table 5a) than the styreneincorporation in the products produced by the combinations of the sameancillary ligands with zirconium precursors.

As stated herein, a solution process is specified for certain benefits,with the solution process being run at a temperature above 90° C., morespecifically at a temperature above 100° C., further more specificallyat a temperature above 110° C. and even further more specifically at atemperature above 130° C. Suitable solvents for polymerization arenon-coordinating, inert liquids. Examples include straight andbranched-chain hydrocarbons such as isobutane, butane, pentane,isopentane, hexane, isohexane, heptane, octane, Isopar-E® and mixturesthereof, cyclic and alicyclic hydrocarbons such as cyclohexane,cycloheptane, methylcyclohexane, methylcycloheptane, and mixturesthereof, perhalogenated hydrocarbons such as perfluorinated C₄₋₁₀alkanes, chlorobenzene, and aromatic and alkylsubstituted aromaticcompounds such as benzene, toluene, mesitylene, and xylene. Suitablesolvents also include liquid olefins which may act as monomers orcomonomers including ethylene, propylene, 1-butene, butadiene,cyclopentene, 1-hexene, 1-pentene, 3-methyl-1-pentene,4-methyl-1-pentene, 1,4-hexadiene, 1-octene, 1-decene, isobutylene,styrene, divinylbenzene, allylbenzene, and vinyltoluene (including allisomers alone or in admixture). Mixtures of the foregoing are alsosuitable.

In some embodiments, a solution process is specified for crystallinepolypropylene production. The solution process to prepare isotacticpolypropylene comprises adding a catalyst and propylene monomer to areactor and subjecting the contents to polymerization conditions, suchthat polypropylene is obtained that has a crystallinity index value thatdoes not vary by more than about 0.1, when the temperature of thesolution process is varied from a temperature below 90° C. to atemperature above 100° C. In some embodiments in this section, the lowertemperature is between about 70° C. and about 90° C. (or between about75° C. and about 95° C. or between about 80° C. and about 95° C.) andthe higher temperature is between about 100° C. and 110° C. (or betweenabout 105° C. and about 115° C., or between about 100° C. and about 115°C.). In this context, the solution process can be run at a temperatureand pressure that produce a desired product, but generally, the solutionprocess temperature is above 100° C. and more specifically above 110°C., while maintaining a high crystallinity index value and highmolecular weight. This solution polymerization process also maintainsthe melting point of the polypropylene, such that it does not vary bymore than 10° C., when the temperature of the solution process is variedfrom a temperature below 90° C. to a temperature above 100° C. In thiscontext, the solution process can be run at a temperature and pressurethat produce a desired product, but generally, the solution processtemperature is above 100° C. and more specifically above 110° C., whilemaintaining a melting point above 135° C. (and if desired below about155° C.). Also, in this solution process, the process temperature may beat least 110° C. while producing polypropylene that has a weight averagemolecular weight of at least 100,000, more preferably at least about300,000. In alternative embodiments the stated properties of the polymerare maintained when the temperature of the solution process is variedfrom a temperature below about 95° C. to a temperature above 105° C. orfrom a temperature below 85° C. to a temperature above 105° C. As withthe above, these alternative embodiments have a lower temperature limitof about 70° C. and an upper temperature limit of about 115° C. Thepolypropylene properties are made in a process that does not requireseparation or fractionation of a product into component products (suchas separation of atactic polypropylene from crystalline polypropylene,as is known in the art). Thus, in addition, the properties are measuredon the bulk sample. Otherwise, the solution process may be run in accordwith methods known to those of skill in the art.

Combinatorial Methodology

The ligands, metal-ligand complexes and compositions of this inventioncan be prepared and tested for catalytic activity in one or more of theabove reactions in a combinatorial fashion. Combinatorial chemistrygenerally involves the parallel or rapid serial synthesis and/orscreening or characterization of compounds and compositions of matter.U.S. Pat. Nos. 5,985,356, 6,030,917 and WO 98/03521, all of which areincorporated herein by reference, generally disclose combinatorialmethods. In this regard, the ligands, metal-ligand complexes orcompositions may be prepared and/or tested in rapid serial and/orparallel fashion, e.g., in an array format. When prepared in an arrayformat, ligands, metal-ligand complexes or compositions may be take theform of an array comprising a plurality of compounds wherein eachcompound can be characterized by any of the above general formulas(i.e., I, A, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII orXIV). An array of ligands may be synthesized using the proceduresoutlined previously. The array may also be of metal precursor compounds,the metal-ligand complexes or compositions characterized by thepreviously described formulae and/or description. Typically, each memberof the array will have differences so that, for example, a ligand oractivator or metal precursor or R group in a first region of the arraymay be different than the ligand or activator or metal precursor or Rgroup in a second region of the array. Other variables may also differfrom region to region in the array.

In such a combinatorial array, typically each of the plurality ofcompositions or complexes has a different composition or stoichiometry,and typically each composition or complex is at a selected region on asubstrate such that each compound is isolated from the othercompositions or complexes. This isolation can take many forms, typicallydepending on the substrate used. If a flat substrate is used, there maysimply be sufficient space between regions so that there cannot beinterdiffusion between compositions or complexes. As another example,the substrate can be a microtiter or similar plate having wells so thateach composition or complex is in a region separated from othercompounds in other regions by a physical barrier. The array may alsocomprise a parallel reactor or testing chamber.

The array typically comprises at least 8 compounds, complexes orcompositions each having a different chemical formula, meaning thatthere must be at least one different atom or bond differentiating themembers in the array or different ratios of the components referred toherein (with components referring to ligands, metal precursors,activators, group 13 reagents, solvents, monomers, supports, etc.). Inother embodiments, there are at least 20 compounds, complexes orcompositions on or in the substrate each having a different chemicalformula. In still other embodiments, there are at least 40 or 90 or 124compounds, complexes or compositions on or in the substrate each havinga different chemical formula. Because of the manner of formingcombinatorial arrays, it may be that each compound, complex orcomposition may not be worked-up, purified or isolated, and for example,may contain reaction by-products or impurities or unreacted startingmaterials.

The catalytic performance of the compounds, complexes or compositions ofthis invention can be tested in a combinatorial or high throughputfashion. Polymerizations can also be performed in a combinatorialfashion, see, e.g., U.S. patent application Ser. No. 09/239,223, filedJan. 29, 1999; U.S. Pat. No. 6,306,658 and WO 00/09255, each of which isherein incorporated by reference.

EXAMPLES

General: All reactions were performed under a purified argon or nitrogenatmosphere in a Vacuum Atmospheres glove box. All solvents used wereanhydrous, de-oxygenated and purified according to known techniques. Allligands and metal precursors were prepared according to procedures knownto those of skill in the art, e.g., under inert athmosphere conditions,etc. Ethylene/styrene and ethylene/1-octene copolymerizations andpropylene polymerizations were carried out in a parallel pressurereactor, which is fully described in pending U.S. patent applicationsSer. No. 09/177,170, filed Oct. 22, 1998, Ser. No. 09/239,223, filedJan. 29, 1999, and WO 00/09255, and U.S. Pat. No. 6,306,658 each ofwhich is incorporated herein by reference.

High temperature Size Exclusion Chromatography was performed using anautomated “Rapid GPC” system as described in U.S. Pat. Nos. 6,175,409,6,260,407, and 6,294,388 each of which is incorporated herein byreference. In the current apparatus, a series of two 30 cm×7.5 mm linearcolumns, with one column containing PLgel 10 um, MixB and the othercolumn containing PLgel 5 um, MixC (available from Polymer Labs). TheGPC system was calibrated using narrow polystyrene standards. The systemwas operated at a eluent flow rate of 1.5 mL/min and an oven temperatureof 160° C. o-dichlorobenzene was used as the eluent. The polymer sampleswere dissolved 1,2,4-trichlorobenzene at a concentration of about 1mg/mL. Between 40 μL and 200 μL of a polymer solution were injected intothe system. The concentration of the polymer in the eluent was monitoredusing an evaporative light scattering detector. All of the molecularweight results obtained are relative to linear polystyrene standards.

The ratio of 1-octene to ethylene incorporated in the ethylene-octenecopolymer products was determined by FTIR. FTIR was performed on aBruker Equinox 55+IR Scope II in reflection mode using a Pike MappIRaccessory with 16 scans. The ratio of 1-octene to ethylene incorporationwas represented as the weight % (wt. %) of 1-octene incorporated in thepolymer (wt. % 1-octene). Wt. % 1-octene was obtained from ratio of bandheights at 1378 cm⁻¹ and 4335 cm⁻¹. This method was calibrated using aset of ethylene/1-octene copolymers with a range of known wt. % 1-octenecontent.

Crystallinity in polypropylene was determined by FTIR spectroscopy. FTIRspectra of thin films deposited from solution onto gold coated Si wafersare acquired at 4 cm⁻¹ resolution and with 16 scans inreflection-absorption mode on a Bruker Equinox 55 FTIR spectrometerequipped with a Pike MappIR accessory. The height ratio of two bands at995 cm⁻¹ (C—H bending and CH₃ rocking mode from regular crystallineisotactic helices) and 972 cm⁻¹ (coupled C—C stretching and CH₃ rockingmode, independent of crystallinity) is determined as a measure ofisotacticity (as known in the art, see, e.g., J. P. Luongo, J. Appl.Polym. Sci 3 (1960) 302-309, and T. Sundell, H. Fagerholm, H. Crozier,Polymer 37 (1996) 3227-3231, each of which is incorporated herein byreference). For blends of atactic and isotactic polypropylene (PP) with0-70% isotactic PP, the IR ratio is proportional to the percentage ofisotactic PP. For greater than 98% isotactic PP the ratio is greaterthan 0.95, for amorphous PP the ratio is 0.2.

The ratio of styrene to ethylene incorporated in the polymer products,represented as the mol % of styrene incorporated in the polymer (mol %styrene) was determined using FTIR spectroscopy. The IR spectra (16scans at 4 cm⁻¹ resolution) analyzed by Partial Least Squares (PLS)analysis with PLSplus/IQ V3.04 for GRAMS/32 (Galactic Industries)software, using the following training set for calibration.

Training Set

The analysis based on a training set consisting of 180 spectra of blendsof ethylene-styrene copolymers with known styrene incorporation, andatactic homo-polystyrene. The 16 known copolymers had between 1 and 47mol % incorporated styrene. The atactic homo-polystyrene content in theblends ranged from 0 to 90% of the total styrene content of the blend.Most blends are prepared from copolymers with up to 20 mol %incorporation. Multiple spectra per blend were included in the trainingset.

Preprocessing of the Spectra

Mean centering; linear baseline correction based on average absorbancesat 2074 cm⁻¹-2218 cm⁻¹ and 3224 cm⁻¹-3465 cm⁻¹; thickness correctionbased on band area from 1483 cm⁻¹ to 1504 cm⁻¹ with baseline from 1389cm⁻¹-1413 cm⁻¹ to 1518 cm⁻¹-1527 cm⁻¹.

Analysis

PLS-1 algorithm; spectral regions 499 cm⁻¹ to 2033 cm⁻¹ and 3577 cm⁻¹ to4495 cm⁻¹. Prediction of number ratios of atactic homo-polystyrene tototal styrene (∝ % atactic homo-polystyrene to total styrene) with 10factors and ethylene to total styrene (∝ mol % total styrene) with 7factors and calculation of mol % incorporated styrene from these 2numbers.

The ratio of styrene to ethylene incorporated in the polymer products,represented as the weight % (wt. %) of styrene incorporated in thepolymer (wt. % styrene) can also be determined using ¹H NMRspectroscopy.

Differential Scanning Calorimetry (DSC) measurements were performed on aTA instrument DSC 2920 to determine the melting point of polymers. Thesample was equilibrated at 200° and held for 4 minutes. The sample wascooled with a rate of 10° C. per minute to 55° C. where it was held for10 minutes. The sample was cooled further to −50° C. with a rate of 10°C./min and held at −50° C. for 4 minutes. Then, the sample was heated to200° C. at a rate of 1° C./min and data were collected during thatheating period.

Ethylene/isobutylene copolymerizations were carried out in a parallelpressure reactor equipped with a magnetic stirrer hotplate. The ratio ofisobutylene to ethylene incorporated in the polymer products,represented as the weight % (wt. %) of isobutylene incorporated in thepolymer (wt. % IB) was determined using ¹H NMR spectroscopy.

The following ligands are used in some of these examples:

These ligands were prepared using techniques known to those of skill inthe art, for example, using the following general experimental:

Part A: Synthesis of 2-bromo-6-formylpyridine

To a solution of 23.7 g (100 mmol) of 2,6-dibromopyridine in 150 mL ofanhydrous, degassed THF cooled to −78° C. was added dropwise under N₂ asolution of 11.0 mL (110 mmol) of 10.0 M ^(n)BuLi in 150 mL ofanhydrous, degassed Et₂O. After 2 h at −78° C., 24.2 mL (300 mmol) ofanhydrous, degassed DMF was added dropwise with rapid stirring. Thissolution was stirred at −78° C. for 2 h, then allowed to warn to RTovernight.

The solution was cooled to −78° C. and 100 mL of 1.0 M aq. HCl was addedslowly. The organic phase was separated and the aqueous phase was washedwith 3×50 mL Et₂O. The organic washes were combined and washed with 3×50mL H₂O and 3×50 mL brine, then dried over Na₂SO₄. The volatiles wereremoved in vacuo to provide an orange oil. The oil was triturated withhexanes to give a pale orange solid that was washed with cold pentaneand dried under vacuum overnight.

Part B: Synthesis of 2-formyl-6-naphthylpyridine

Naphthylboronic acid (2.06 g, 12 mmol) and Na₂CO₃ (2.65 g, 25 mmol) weredissolved in 60 mL of degassed 4:1 H₂O/MeOH. This solution was added viacannula to a solution of 1.86 g (10 mmol) of 2-bromo-6-formylpyridineand 116 mg (0.10 mmol) of Pd(PPh₃)₄ in 50 mL of degassed toluene. Thebiphasic solution was vigorously stirred and heated to 70° C. under N₂for 4 h. On cooling to RT, the organic phase was separated and washedwith 3×25 mL of Et₂O. The combined organic extracts were washed with3×25 mL of H₂O and 1×20 mL of brine and dried over Na₂SO₄. Afterremoving the volatiles in vacuo, the resultant brown oil waschromatographed on silica with 0-50% hexanes/CH₂Cl₂. The early fractionscontained naphthalene and binaphthyl and were discarded. The remainingfractions were combined and the volatiles were removed to provide2-formyl-6-naphthlypyridine as a white solid.

Part C: Synthesis of 6-naphthylpyridine-2-(2,6-diisopropylphenyl)imine

A solution of 1.17 g (0.5 mmol) of 2-formyl-6-naphtlypyridine and 0.98 g(0.55 mmol) of 2,6-diisopropylaniline in 50 mL of anhydrous THFcontaining 3 Å sieves and a catalytic amount of TsOH was heated toreflux under N₂ for 12 h. After filtration and removal of the volitilesin vacuo, the crude material was passed through a 4×6 cm plug of neutralalumina with 1:1 hexanes/CH₂Cl₂ eluent. Removal of the volitilesprovided 6-naphthylpyridine-2-(2,6-diisopropylphenyl)imine as yellowcrystals.

Part D: Synthesis of(6-naphthyl-2-pyridyl)-N-(2,6-diisopropylphenyl)benzylamine (Ligand L4)

Synthesis with MgBr₂ Precomplexation

To a well-stirred slurry of powdered MgBr₂ (184 mg, 1 mmol) in 2 mL ofanhydrous, degassed Et₂O was added under N₂ a solution of6-naphthylpyridine-2-(2,6-diisopropylphenyl)imine (392 mg, 1 mmol) in 2mL of Et₂O. The mixture was sonicated until the yellow color of theimine dissipated and a free-flowing pale yellow powder was formed. Tothis suspension was added with vigorous stirring a solution ofphenyllithium (833 uL of 1.8 M in cyclohexane, 1.5 mmol). After stirringat RT for 12 h, the reaction was quenched with aq. NH₄Cl. The organiclayer was separated, washed with brine and H₂O, then dried over Na₂SO₄.Following chromatography (silica gel, 3% THF/hexanes), the product wasisolated as a colorless oil.

Synthesis without MgBr₂ Precomplexation

To a solution of 6-naphthylpyridine-2-(2,6-diisopropylphenyl)imine (392mg, 1 mmol) in 5 mL of anhydrous, degassed Et₂O cooled to −30° C. underN₂ was added a solution of phenyllithium (833 uL of 1.8 M incyclohexane, 1.5 mmol). After warming to RT over 1 h. the soln. wasstirred at RT for 12 h. The reaction was then quenched with aq. NH₄Cl,and worked-up as above.

This same procedure is followed for the different ligands, but with thefollowing different starting materials for the different ligands:

In part B:

For ligand L28, the last step in the reaction sequence (part D) is areduction reaction using sodiumtriacetozyborohydride (Na(Oac)₃BH) in THFfor 1-3 days following aq. NH₄Cl quench and work-up as it is describedin Part D above.

Example 1 Synthesis of Ligand

Both Parts to this Example Make the Same Ligand, Shown Above, With andWithout the Presence of Complexing Agent.

Part A: Synthesis without MgBr₂ Complexation

To a solution of 2-pyridyl-N-mesitylimine (224 mg, 1 mmol) in 5 mL ofanhydrous, degassed Et₂O cooled to −30°C.□was□added□under□argon□a□solution□of□ phenyllithium (833 μL of 1.8 Min cyclohexane, 1.5 mmol). After warming to room temperature over 1hour, the solution was stirred for a further 12 hours. The reaction wasthen quenched with aqueous NH₄Cl, the layers were separated, and theorganic layer was dried over Na₂SO₄. GC-MS analysis showed a mixture ofthe C- and N-alkylated products. The C- to N-alkylation ratio was 4:1 asdetermined by ¹H NMR.

Part B: Synthesis with MgBr₂ Complexation

To a stirred slurry of powdered MgBr₂ (92 mg, 0.5 mmol) in 1 mL ofanhydrous, degassed Et₂O was added under argon a solution of2-pyridyl-N-mesitylimine (224 mg, 1 mmol) in 5 mL of Et₂O. The mixturewas stirred for 2 hours until the yellow color of the imine dissipatedand a pale yellow solid was formed. After cooling to −30°C.,□a□solution□ of phenyllithium (833 μL of 1.8 M in cyclohexane, 1.5mmol) was added with stirring. After warming to room temperature over 1hour, the solution was stirred for a further 12 hours. The reaction wasworked up as above. GC-MS analysis showed exclusive formation of theC-alkylated product. Following chromatography (silica, 10% ethylacetate/hexanes), the product was isolated as a colorless solid (266 mg,88%).

Examples 2-3

Preparation of the polymerization reactor prior to injection of catalystcomposition; Ethylene-1-octene Polymerizations: A pre-weighed glass vialinsert and disposable stirring paddle were fitted to each reactionvessel of the reactor. The reactor was then closed, 0.100 mL of a 0.02 Msolution of triisobutylaluminium (TIBA) in toluene, then 2.375 mL oftoluene, then 0.250 mL of 1-octene, then 2.375 mL of toluene, wereinjected into each pressure reaction vessel through a valve. Thetemperature was then set to 130° C., and the toluene/1-octene mixturewas exposed to ethylene gas at 100 psi pressure. An ethylene pressure of100 psi in the pressure cell and the temperature setting weremaintained, using computer control, until the end of the polymerizationexperiment.

Preparation of the polymerization reactor prior to injection of catalystcomposition; Ethylene-Styrene Polymerizations: A pre-weighed glass vialinsert and disposable stirring paddle were fitted to each reactionvessel of the reactor. The reactor was then closed, 0.100 mL of a 0.02 Msolution of triisobutylaluminium (TIBA) in toluene, then 4.50 mL oftoluene, were injected into each pressure reaction vessel through avalve. The temperature was then set to 110° C., and the toluene mixturewas exposed to ethylene gas at 100 psi pressure. An ethylene pressure of100 psi in the pressure cell and the temperature setting weremaintained, using computer control, until the end of the polymerizationexperiment.

Ethylene-1-octene and Ethylene-Styrene Polymerizations: Thepolymerization reactions were allowed to continue for 30 minutes, duringwhich time the temperature and pressure were maintained at their pre-setlevels by computer control. After 30 minutes, the ethylene flow to thereactor vessel was stopped. The temperature was then allowed to drop tobelow 80° C. and the ethylene pressure in the cell was vented.

Product work up: Ethylene-1-octene Polymerizations After thepolymerization reaction, the glass vial insert, containing the polymerproduct and solvent, was removed from the pressure cell and removed fromthe inert atmosphere dry box, and the volatile components were removedusing a centrifuge vacuum evaporator. After most of the volatilecomponents had evaporated, the vial contents were dried thoroughly byevaporation at elevated temperature under reduced pressure. The vial wasthen weighed to determine the yield of polymer product. The polymerproduct was then analyzed by rapid GPC, as described above to determinethe molecular weight of the polymer produced, and by FTIR spectroscopyto determine the ratio of 1-octene to ethylene incorporated in thepolymer product, represented as the weight % of 1-octene incorporated inthe polymer.

Product work up: Ethylene-Styrene Polymerizations After thepolymerization reaction, the glass vial insert, containing the polymerproduct and solvent, was removed from the pressure cell and removed fromthe inert atmosphere dry box, and the volatile components were removedusing a centrifuge vacuum evaporator. After most of the volatilecomponents had evaporated, the vial contents were dried thoroughly byevaporation at elevated temperature under reduced pressure. The vial wasthen weighed to determine the yield of polymer product. The polymerproduct was then analyzed by rapid GPC, as described above to determinethe molecular weight of the polymer produced, and by ¹H NMR spectroscopyto determine the ratio of styrene to ethylene incorporated in thepolymer product, represented as the weight % of styrene incorporated inthe copolymer.

Presentation of results: Tables 3-5 present results from libraries ofpolymerizations, using the following key (Tables 3 and 4 are in FIGS. 3and 4, respectively):

Example 2 Ethylene-1-octene Polymerizations Using Hafnium-LigandCompositions

Preparation of Stock Solutions: The “group 13 reagent solution” is a0.20 M solution of triisobutylaluminium (TIBA). The “activator solution”is a 10 mM solution of N,N′-dimethylaniliniumtetrakis(pentafluorophenyl)borate in toluene (160 mg in 20 mL toluene),heated to approximately 85° C. to fully dissolve theN,N′-dimethylanilinium tetrakis(pentafluorophenyl)borate.

In situ preparation of Hafnium-ligand compositions: Stock solutions wereprepared as follows: The “metal precursor solution” is a 25 mM solutionof Hf(CH₂C₆H₅)₄ in toluene (34 mg in 2.50 mL toluene; HfCl₄ waspurchased from Strem Chemicals, Inc., Newburyport, Mass. (99.95%+Hf) andmodified with 4 equivalents of benzyl Gringard at −30° C. in ether). The“ligand solutions” are a 25 mM solution the respective ligands intoluene, prepared in an array of 1 mL glass vials by adding 0.060 mL oftoluene to 1.5 μmol of the ligand in a 1 mL glass vial. To each 1 mLglass vial containing ligand/toluene solution was added 0.060 mL of themetal precursor solution (1.5 μmol), to form the metal-ligandcombination solution. To each metal-ligand combination solution was thenadded 0.060 mL of a 0.5 M 1-octene solution in toluene (30 μmol of1-octene). The resultant solutions we allowed to sit at room temperaturefor 1 hour prior to addition of TIBA solution and injection into thereactor, as described below. Table 3 illustrates the hafnium-ligandsolutions prepared in this example.

Injection of solutions into the pressure reactor vessel: After thetoluene/1-octene mixture was saturated with ethylene at 100 psipressure, 0.075 mL (15 μmol) of the group 13 reagent solution was addedto the 1 mL vial. About 30 seconds later, 0.100 mL (1.0 μmol) of the“activator solution” followed immediately by 0.400 mL of toluene, wereinjected into the reaction vessel. About another 30 seconds later, 0.170mL of the 1 mL vial contents, followed immediately by 0.330 mL oftoluene, were injected into the reaction vessel. Results are presentedin Table 3, which is presented in FIG. 3.

Comparative Example Ethylene-1-octene Polymerizations UsingZirconium-Ligand Compositions

Preparation of Stock Solutions: The “group 13 reagent solution” is a0.20 M solution of triisobutylaluminium (TIBA). The “activator solution”is a 10 mM solution of N,N′-dimethylaniliniumtetrakis(pentafluorophenyl)borate in toluene (160 mg in 20 mL toluene),heated to approximately 85° C. to fully dissolve theN,N′-dimethylanilinium tetrakis(pentafluorophenyl)borate.

In situ preparation of Zirconium-ligand compositions: Stock solutionswere prepared as follows: The “metal precursor solution” is a 25 mMsolution of Zr(CH₂C₆H₅)₄ in toluene (28.5 mg in 2.50 mL toluene). The“ligand solutions” are a 25 mM solution the respective ligands intoluene, prepared in an array of 1 mL glass vials by adding 0.060 mL oftoluene to 1.5 μmol of the ligand in a 1 mL glass vial. To each 1 mLglass vial containing ligand/toluene solution was added 0.060 mL of themetal precursor solution (1.5 μmol), to form the metal-ligandcombination solution. To each metal-ligand combination solution was thenadded 0.060 mL of a 0.5 M 1-octene solution in toluene (30 μmol of1-octene). The resultant solutions were allowed to sit at roomtemperature for 1 hour prior to addition of TIBA solution and injectioninto the reactor, as described below. Table 4 illustrates thezirconium-ligand solutions prepared in this comparative example.

Injection of solutions into the pressure reactor vessel: After thetoluene/1-octene mixture was saturated with ethylene at 100 psipressure, 0.075 mL (15 μmol) of the group 13 reagent solution was addedto the 1 mL vial. About 30 seconds later, 0.100 mL (1.0 μmol) of the“activator solution” followed immediately by 0.400 mL of toluene, wereinjected into the reaction vessel. About another 30 seconds later, 0.170mL of the 1 mL vial contents, followed immediately by 0.330 mL oftoluene, were injected into the reaction vessel. Results are presentedin Table 4, which is presented in FIG. 4.

Example 3 Ethylene-Styrene Polymerizations Using Hafnium-LigandCompositions

Preparation of Stock Solutions: The “group 13 reagent solution” is a0.20 M solution of triisobutylaluminium (TIBA). The “activator solution”is a 10 mM solution of N,N′-dimethylaniliniumtetrakis(pentafluorophenyl)borate in toluene (160 mg in 20 mL toluene),heated to approximately 85° C. to fully dissolve theN,N′-dimethylanilinium tetrakis(pentafluorophenyl)borate.

In situ preparation of Hafnium-ligand compositions: Stock solutions wereprepared as follows: The “metal precursor solution” is a 25 mM solutionof Hf(CH₂C₆H₅)₄ in toluene (34 mg in 2.50 mL toluene; HfCl₄ waspurchased from Strem Chemicals, Inc., Newburyport, Mass. (99.95%+Hf) andmodified with 4 equivalents of benzyl Gringard at −30° C. in ether). The“ligand solutions” are a 25 mM solution the respective ligands intoluene, prepared in an array of 1 mL glass vials by adding 0.060 mL oftoluene to 1.5 μmol of the ligand in a 1 mL glass vial. To each 1 mLglass vial containing ligand/toluene solution was added 0.060 mL of themetal precursor solution (1.5 μmol), to form the metal-ligandcombination solution. To each metal-ligand combination solution was thenadded 0.060 mL of a 0.5 M 1-octene solution in toluene (30 μmol of1-octene). The resultant solutions were allowed to sit at roomtemperature for 1 hour prior to addition of TIBA solution and injectioninto the reactor, as described below. Table 5 illustrates thehafnium-ligand solutions prepared.

Injection of solutions into the pressure reactor vessel: After thetoluene mixture was saturated with ethylene at 100 psi pressure, 0.500mL of styrene followed immediately by 0.500 mL of toluene, were injectedinto the pressure reaction vessel. About 30 seconds later, 0.075 mL (15μmol) of the group 13 reagent solution was added to the 1 mL vial. Aboutanother 30 seconds later, 0.100 mL (1.0 μmol) of the “activatorsolution” followed immediately by 0.400 mL of toluene, were injectedinto the reaction vessel. About another 30 seconds later, 0.170 mL ofthe 1 mL vial contents, followed immediately by 0.330 mL of toluene,were injected into the reaction vessel. Results are presented in Table5.

Comparative Example Ethylene-Styrene Polymerizations UsingZirconium-Ligand Compositions

Preparation of Stock Solutions: The “group 13 reagent solution” is a0.20 M solution of triisobutylaluminium (TIBA). The “activator solution”is a 10 mM solution of N,N′-dimethylaniliniumtetrakis(pentafluorophenyl)borate in toluene (160 mg in 20 mL toluene),heated to approximately 85° C. to fully dissolve theN,N′-dimethylanilinium tetrakis(pentafluorophenyl)borate.

In situ preparation of zirconium-ligand compositions: Stock solutionswere prepared as follows: The “metal precursor solution” is a 25 mMsolution of Zr(CH₂C₆H₅)₄ in toluene (28.5 mg in 2.50 mL toluene). The“ligand solutions” are a 25 mM solution the respective ligands intoluene, prepared in an array of 1 mL glass vials by adding 0.060 mL oftoluene to 1.5 μmol of the ligand in a 1 mL glass vial. To each 1 mLglass vial containing ligand/toluene solution was added 0.060 mL of themetal precursor solution (1.5 μmol), to form the metal-ligandcombination solution. To each metal-ligand combination solution was thenadded 0.060 mL of a 0.5 M 1-octene solution in toluene (30 μmol of1-octene). The resultant solutions was allowed to sit at roomtemperature for 1 hour prior to addition of TIBA solution and injectioninto the reactor, as described below. Table 5 illustrates thezirconium-ligand solutions prepared:

Injection of solutions into the pressure reactor vessel: After thetoluene mixture was saturated with ethylene at 100 psi pressure, 0.500mL of styrene followed immediately by 0.500 mL of toluene, were injectedinto the pressure reaction vessel. About 30 seconds later, 0.075 mL (15μmol) of the group 13 reagent solution was added to the 1 mL vial. Aboutanother 30 seconds later, 0.100 mL (1.0 μmol) of the “activatorsolution” followed immediately by 0.400 mL of toluene, were injectedinto the reaction vessel. About another 30 seconds later, 0.170 mL ofthe 1 mL vial contents, followed immediately by 0.330 mL of toluene,were injected into the reaction vessel. Results are presented in Table5.

TABLE 5 Hf(CH₂C₆H₅)₄ and Zr(CH₂C₆H₅)₄-Ligand Compositions: Ethylene-Styrene Copolymerization Results: Zr(CH₂C₆H₅)₄ Hf(CH₂C₆H₅)₄ Yield wt. %Styrene Yield wt. % Styrene Ligand (mg) by NMR (mg) by NMR

152 6 469 14

209 7 326 15

138 7 295 15

163 7 278 10

134 6 153 15

Example 3A Ethylene-Styrene Polymerizations Using Hafnium-LigandCompositions

This example comprises four polymerization reactions carried out withdifferent ligand/hafnium compositions for the copolymerization ofethylene and styrene. The results are summarized in Table 5A, along withfour comparative examples of polymerization reactions carried out withdifferent ligand/zirconium compositions for the copolymerization ofethylene and styrene.

Preparation of the polymerization reactor prior to injection of catalystcomposition: A pre-weighed glass vial insert and disposable stirringpaddle were fitted to each reaction vessel of the reactor. The reactorwas then closed, 0.10 mL of a 0.02 M solution ofdiisobutylaluminiumhydride (“DIBAL”) in toluene and 3.8 mL of toluenewere injected into each pressure reaction vessel through a valve. Thetemperature was then set to 110° C., and the stirring speed was set to800 rpm, and the mixture was exposed to ethylene at 100 psi pressure. Anethylene pressure of 100 psi in the pressure cell and the temperaturesetting were maintained, using computer control, until the end of thepolymerization experiment.

Preparation of the group 13 reagent and activator stock solutions: The“activator solution” is a 5 mM solution of N,N′-dimethylaniliniumtetrakis (pentafluorophenyl) borate in toluene (“ABF20”). The solutionis heated to approximately 85° C. to dissolve the reagent. The group 13reagent solution is a 0.2 M solution of diisobutylaluminiumhydride(“DIBAL”) in toluene.

In situ preparation of metal-ligand compositions: Stock solutions wereprepared as follows: The “metal precursor solution” is a 10 mM solutionof Hf(NMe₂)₄ in toluene. The “ligand solutions” are 25 mM solutions ofthe representative ligands in toluene, prepared in an array of 1 mLglass vials by dispensing 0.030 mL of a 25 mM ligand solution in a 1 mLglass vial. To each 1 mL glass vial containing ligand/toluene solutionwas added 0.075 mL of the metal precursor solution (0.75 μmol), to formthe metal-ligand combination solution. The reaction mixtures we allowedto sit at 80° C. for 2-3 hours during which time most of the solventevaporates. The reaction mixtures were dried completely by blowing astream of Argon over the 1 mL vial. Prior to addition of alkylation andactivator solution, a small amount of solvent (0.020 mL) was added tothe dry composition.

Activation and Injection of solutions into the pressure reactor vessel:To the ligand metal composition, 0.037 mL of a 500 mM solution of1-octene in toluene and 0.020 mL of toluene and 0.112 mL of the group 13reagent solution was added to the 1 mL vial. Around 11 min later, 0.420mL of styrene followed immediately by 0.380 mL of toluene, were injectedinto the prepressurized reaction vessel. Another 1 min later, 0.165 mL(0.845 μmol) of the “activator solution” was added to the 1 mL vial.About another 30 seconds later, 0.181 mL of the 1 mL vial contents,followed immediately by 0.619 mL of toluene, were injected into thereaction vessel.

Polymerization: The polymerization reaction was allowed to continue forthe 217-601 seconds, during which time the temperature and pressure weremaintained at their pre-set levels by computer control. Thepolymerization times were the lesser of the maximum desiredpolymerization reaction time or the time taken for a predeterminedamount of monomer gas to be consumed in the polymerization reaction. Thespecific times for each polymerization are shown in table 5B the columntitled Hf(NMe₂)₄. After the reaction time elapsed, the reaction wasquenched by addition of an overpressure of carbon dioxide.

Product work up: ethylene/styrene copolymerizations After thepolymerization reaction, the glass vial insert, containing the polymerproduct and solvent, was removed from the pressure cell and removed fromthe inert atmosphere dry box, and the volatile components were removedusing a centrifuge vacuum evaporator. After most of the volatilecomponents had evaporated, the vial contents were dried thoroughly byevaporation at elevated temperature under reduced pressure. The vial wasthen weighed to determine the yield of polymer product. The polymerproduct was then analyzed by rapid GPC, as described above to determinethe molecular weight of the polymer produced, and by FTIR spectroscopyto determine the styrene incorporation. Results are presented in Table5A in the column titled Hf(NMe₂)₄.

Comparative Example Ethylene-Styrene Polymerizations UsingZirconium-Ligand Compositions:

Preparation of the polymerization reactor prior to injection of catalystcomposition: This part of the experiment was performed as describedabove for Example 3A using Hafnium-ligand compositions.

Preparation of the group 13 reagent and activator stock solutions: Thispart of the experiment was performed as described above for Example 3Ausing Hafnium-ligand compositions.

In situ preparation of metal-ligand compositions: This part of theexperiment was performed as described above for Example 3A usingHafnium-ligand compositions except that the “metal precursor solution”is a 10 mM solution of Zr(NMe₂)₄ in toluene.

Activation and Injection of solutions into the pressure reactor vessel:This part of the experiment was performed as described above for Example3A using Hafnium-ligand compositions.

Polymerization: This part of the experiment was performed as describedabove for Example 3A using Hafnium-ligand compositions, except that thepolymerization reaction was allowed to continue for the 399-600 seconds.The specific times for each polymerization are shown in table 5B in thecolumn titled Zr(NMe₂)₄.

Product work up: ethylene/styrene copolymerizations: This part of theexperiment was performed as described above for Example 3A usingHafnium-ligand compositions. Results are presented in Table 5A in thecolumn titled Zr(NMe₂)₄.

TABLE 5A Hf(NMe₂)₄ and Zr(NMe₂)₄-Ligand Compositions: Ethylene-StyreneCopolymerization Results (Example 3A): Hf(NMe₂)₄ Zr(NMe₂)₄ mol% mol%styrene styrene Ligand Activity (FTIR) Activity (FTIR) L29 57 2.8 23 0.8L30 158 3.0 77 2.0 L4  111 3.1 35 1.6 L5  57 3.3 41 1.9

In Table 5A, Activity is shown in units of mg polymer per minute perμmol of Hf or Zr, mol % styrene is as determined by FTIR using PLSanalysis, as described above.

TABLE 5B Polymerization times in seconds for example 3A Hf(NMe₂)₄Zr(NMe₂)₄ Polymerization Polymerization Ligand time time L29 601 600 L30217 399 L4  293 600 L5  601 601

Example 4 Ethylene-Isobutylene Copolymerizations Using Hafnium-LigandCompositions

Preparation of Stock Solutions: The “group 13 reagent solution” is a 20mM solution of triethylaluminum (TEAL). The “activator solution” is a 5mM solution of N,N′-dimethylanilinium tetrakis(pentafluorophenyl)boratein toluene (75 mg in 20 mL toluene), heated to approximately 85° C. tofully dissolve the N,N′-dimethylaniliniumtetrakis(pentafluorophenyl)borate. The “metal precursor solution” is a20 mM solution of Hf(CH₂C₆H₅)₄ in toluene (33 mg in 2.0 mL toluene). The“ligand solutions” are 20 mM solutions of the ligand shown below inTable 6 in toluene.

Ethylene-Isobutylene Copolymerizations: Pre-weighed glass vials eachcontaining a disposable magnetic stir bar were placed into the positionsof the reactor block. Using a liquid dispensing robot, 2.9 mL of tolueneare added to these glass vials, followed by 0.180 mL of “ligandsolution” and 0.200 mL of Hf(CH₂C₆H₅)₄ in toluene. These solutions werestirred for 30 minutes at room temperature after which 0.02 mL of a 20mM solution of triethylaluminum (TEAL) in toluene were dispensed intoeach reaction vessel. Following a 10 minute waiting period, 0.700 mL ofa 5 mM solution of N,N′-dimethylaniliniumtetrakis(pentafluorophenyl)borate in toluene were added to each vial.The reactor was then closed, exposed to an ethylene/isobutylene gasmixture (ethylene feed 5 psi/isobutylene feed 10 psi pressure) andplaced on a stirrer hotplate maintained at 50° C. for the duration ofthe experiment. After 60 minutes, the reactor was removed from thestirrer hotplate. The gases were vented from the reactor, the reactoropened and the glass vials removed.

Product work up: Ethylene-Isobutylene Polymerizations: The glass vials,containing the polymer product and solvent, were removed from thereactor and removed from the inert atmosphere dry box, and the volatilecomponents were allowed to evaporate at room temperature in the air.After most of the volatile components had evaporated, the vial contentswere dried thoroughly by evaporation under vacuo. The vial was thenweighed to determine the yield of polymer product. The polymer productwas then analyzed by ¹H NMR spectroscopy to determine the ratio ofisobutylene to ethylene incorporated in the polymer product, representedas the weight % of isobutylene incorporated in the copolymer. Table 6shows a summary of the results:

TABLE 6 Hf(CH₂C₆H₅)₄-Ligand Compositions: Ethylene-IsobutyleneCopolymerization Results: Ligand Yield (mg) Wt. % IB

97 33

Example 5-10 Synthesis of Ligand/Metal Complexes 1-21.

Example 5 Synthesis of Complex 1 (C 1)

The ligand L4 used in this example was prepared in the manner describedabove.

Hf(NMe₂)₄ (291 mg, 0.82 mmol) and L4, from above, (358 mg, 0.76 mmol)were combined in 5 mL C₆D₆. The reaction was heated to 70° C. and ventedoccasionally. Aliquots were analyzed by ¹H NMR every hour until thereaction was complete (3 hours). Solvent was then removed, yielding ayellow glassy solid, which was extracted with hot pentane (20 mL) andfiltered. The volume of the filtrate was reduced to 5 mL and then cooledto −35° C. A yellow microcrystalline powder was collected (439 mg, 74%)¹H NMR (δ C₆D₆). 6.55-7.75 (overlapping m, 17H total, Ar), 5.93, (s, 1H,CHpy), 3.65 (sept, 1H, CH-iPr), 3.31 (sept, 1H, CH-iPr), 2.83 (br s, 6,NMe₂), 2.67 (br s, 6, NMe₂), 2.22 (br s, 6, NMe₂), 1.64 (d, 3H, CHMe₂),1.53 (d, 3H, CHMe₂), 1.23 (d, 3H, CHMe₂), 0.26 (d, 3H, CHMe₂). Crystalssuitable for X-ray analysis were obtained by re-crystallization from hothexane and submitted for single crystal X-ray analysis, which confirmedthe structure shown above.

Example 6 Synthesis of Complex 2 (C 2)

The ligand L5 used in the example was prepared in the manner describedabove.

Hf(NMe₂)₄ (121 mg, 0.34 mmol) and L5, from above, (130 mg, 0.31 mmol)were combined in 5 mL toluene. The reaction was heated to 110° C. andvented occasionally. Aliquots were analyzed by ¹H NMR until the reactionwas complete (24 hours). Solvent was then removed, yielding a yellowglassy solid, which was extracted with hot pentane (20 mL) and filtered.The volume of the filtrate was reduced to 5 mL and then cooled to −35°C. A yellow microcrystalline powder was collected (150 mg; 71%). ¹H NMR(δ C₆D₆). 8.36, 7.69 (d, 1H each, Ar) 6.9-7.5 (overlapping m, 12H total,Ar), 6.55 (d, 1H, Ar) 6.10, (s, 1H, CHpy), 3.50 (sept, 1H, CH-iPr), 3.18(s, 6, NMe₂), 2.88 (s, 6, NMe₂), 1.52 (d, 3H, CHMe₂), 1.39 (d, 3H,CHMe₂), 1.17 (d, 3H CHMe₂), 0.49 (d, 3H, CHMe₂). Crystals suitable forx-ray diffraction were obtained by recrystallization from hot pentaneand submitted for single crystal X-ray analysis, which confirmed thestructure shown above.

Examples 7A and 7B

7A Synthesis of complex 3 (C 3): Complex 1, from Example 5 above, (51mg, 0.065 mmol) was dissolved in 7 mL pentane. The mixture was cooled to−35° C. and a 2.0 M solution of AlMe₃ in toluene (330 μL, 0.66 mmol, 10eq.) was added. A yellow precipitate formed and then redissolved as thereaction was allowed to warm to room temperature. The mixture wasstirred at room temperature for 1 hour, and then the solvent wasremoved. The resulting yellow powder was recrystallized from pentane at−35° C. Yellow microcrystals (25 mg) were collected and dried. A secondcrop yielded an additional 7 mg of crystals. (combined yield=73%) ¹H NMR(C₆D₆). 8.56, 8.23, 7.80, 7.72, 7.46 (d, 1 H each, Ar) 7.0-7.4(overlapping m, 10H total), 6.40 (d, 1H, Ar), 5.92, (s, 1H, CHpy), 3.82(sept, 1H, CH-iPr), 3.27 (sept, 1H, CH-iPr), 1.38 (overlapping two d, 6Htotal, CHMe₂), 1.15 (d, 3H, CHMe2), 0.93 (s, 3H, Hf-Me), 0.65 (s, 3H,Hf-Me), 0.38 (d, 3H, CHMe₂).

7B Synthesis of complex 11 (C 11): In a manner similar to that describedin example 7A, complex 11 was synthesized from complex 10.

Examples 8A-8F

8A: Synthesis of complex 4 (C 4): The ligand used in the example wasprepared in the manner generally described above for L1, shown above.

In a manner similar to that described in example 6, the complex wasprepared from L1, from above, (48 mg, 0.11 mmol) and Hf(NMe₂)₄ (0.12mmol) in C₆D₆. The mixture was heated to 100° C. for 24 hours, and thenrecrystalized from pentane (44 mg, 58%). ¹H NMR was consistent with theformation of the complex whose structure is shown above.

8B: Synthesis of complex 6 (C6): The ligand used in the example wasprepared in the manner generally described above for L5, shown above.

In a manner similar to that described in example 7, complex 6 whosestructure is shown above was prepared from L5, from above, (20 mg, 0.05mmol) and Zr(NMe₂)₄ (13 mg, 0.05 mmol) in C₆D₆. After heating to 100° C.for 24 hours, yellow crystals were obtained by recrystallization frompentane. (yield=15 mg, 50%). ¹H NMR was consistent with the formation ofthe complex.

8C: Synthesis of complex 12 (C 12): In a manner similar to thatdescribed in example 7, complex 12 whose structure is shown above wasprepared from L20, from above.

8D: Synthesis of complex 13 (C 13): In a manner similar to thatdescribed in example 7, complex 13 whose structure is shown above wasprepared from L21, from above.

8E: Synthesis of complex 15 (C 15): In a manner similar to thatdescribed in example 7, complex 12 whose structure is shown above wasprepared from L23, from above.

8F: Synthesis of complex 16 (C 16): In a manner similar to thatdescribed in example 7, complex 12 whose structure is shown above wasprepared from L24, from above.

Examples 9A-9F

9A Synthesis of complex 5: The ligand used in the example was preparedin the manner generally described above for L4, shown above. In a mannersimilar to that described in example 5, the complex whose structure isshown above was prepared from L3, from above, (43 mg, 0.09 mmol) andHf(NMe₂)₄ (56 mg, 0.16 mmol) in C₆D₆. The mixture was heated to 100° C.for 48 hours, and then recrystalized from pentane (46 mg, 66%). ¹H NMRwas consistent with the formation of the complex.

9B Synthesis of complex 7: The ligand used in the example was preparedin the manner generally described above for L4, shown above. In a mannersimilar to that described in example 5, the complex whose structure isshown above was prepared from L7, from above.

9C Synthesis of complex 8: The ligand used in the example was preparedin the manner generally described above for L4, shown above. In a mannersimilar to that described in example 5, the complex whose structure isshown above was prepared from L6, from above.

9D Synthesis of complex 9: The ligand used in the example was preparedin the manner generally described above for L4, shown above. In a mannersimilar to that described in example 5, the complex whose structure isshown above was prepared from L9, from above.

9E Synthesis of complex 10: The ligand used in the example was preparedin the manner generally described above for L4, shown above. In a mannersimilar to that described in example 5, the complex whose structure isshown above was prepared from L8, from above.

9F Synthesis of complex 14: The ligand used in the example was preparedin the manner generally described above for L4, shown above. In a mannersimilar to that described in example 5, the complex whose structure isshown above was prepared from L22, from above.

9G Synthesis of complex 21: The ligand used in the example was preparedin the manner generally described above for L4, shown above. In a mannersimilar to that described in example 5, the complex whose structure isshown above was prepared from L30, from above.

Examples 10A-10D Synthesis of Hafnium Benzyl Complexes C17-C20

10A Synthesis of complex 17 (C 17): The ligand used in the example wasprepared in a manner generally described above for L4, shown above.Ligand L25 (202 mg, 0.53 mmol) was dissolved in 4 mL toluene and solidHf(Bz)₄ (306 mg, 0.56 mmol) was added. The solution was stirred for 1hour. ¹H NMR of an aliquot of the reaction mixture revealed that thereaction was complete. The volume was reduced to 1 mL, and pentane (10mL) was added. A yellow precipitate was collected, washed with pentaneand dried. ¹H NMR was consistent with the proposed formula

10B Synthesis of complex 18 (C 18): The ligand used in the example wasprepared in a manner generally described above for L4, shown above. In amanner similar to that descibed in example 10A, the complex whosestructure is shown above was prepared from L26 and Hf(CH₂Ph)₄ in C₆D₆.

10C Synthesis of complex 19 (C 19): The ligand used in the example wasprepared in a manner generally described above for L4, shown above. In amanner similar to that descibed in example 10A, the complex whosestructure is shown above was prepared from L27 and Hf(CH₂Ph)₄ in C₆D₆.

10D Synthesis of complex 20 (C 20): The ligand used in the example wasprepared in a manner generally described above for L4, shown above. In amanner similar to that descibed in example 10A, the complex whosestructure is shown above was prepared from L28 and Hf(CH₂Ph)₄ in C₆D₆ .

Examples 11-14, 16-24 Presentation of the Results

In the following Examples 11-14 and 16-24, the polymerizations carriedout for the particular example are represented in the first table withineach example. This first table within each example describes theidentity of either ligand (L#) or metal complex (C#) used in eachexperiment represented as entry in the grid framed by the rows andcolumns labeled with letters and numbers respectively. Additionalexperimental details described in the paragraphs: “Preparation of thepolymerization reactor prior to injection of catalyst composition” and“Activation and Injection of solutions into the pressure reactor vessel”such as “group 13 reagent”, t₁, t₂, Injection fraction, Polym. Temp.(abbreviation for polymerization temperature), Premix Temperature andActivator are given in the first table. Experimental details which applyto each experiment in a row of the grid are listed to the right of therow to which they refer. Experimental details which apply to eachexperiment in a column of the grid are listed below the column to whichthey refer.

For example the experiment 11.B.2. employs complex C1, and for thisexample the “group 13 reagent” is TMA, t₁ is 0.5 minutes , t₂ is 10minutes, Injection fraction is 0.066, Polym. Temp. (abbreviation forpolymerization temperature) is 110° C., Premix temperature is 24° C. andActivator is ABF20.

The data in the subsequent tables of each example are also representedin grid format as entries in grids framed by the rows and columnslabeled with letters and numbers respectively, such that the data ineach lettered row and numbered column corresponds to the experimentsdescribed in the corresponding lettered and numbered rows and columns inthe first table of each example. For example the experiment 11.B.2. thereaction time is 217 seconds, the activity is 877 mg polymer per minuteper μmol, the crystallinity index is 0.83 and the weight averagemolecular weight is 163,000 (represented in the table as 163 k).

Example 11 Propylene Polymerizations at 110° C.

Sixteen polymerization experiments were carried out in this example,using different metal complexes, activator amounts, group 13 reagentsand activating conditions.

Preparation of the polymerization reactor prior to injection of catalystcomposition: A pre-weighed glass vial insert and disposable stirringpaddle were fitted to each reaction vessel of the reactor. The reactorwas then closed, 0.10 mL of a 0.02 M solution of group 13 reagents intoluene and 3.9 mL of toluene were injected into each pressure reactionvessel through a valve. The temperature was then set to the appropriatesetting (with specific temperatures for each polymerization being listedin table 7, below), and the stirring speed was set to 800 rpm, and themixture was exposed to propylene at 100 psi pressure. A propylenepressure of 100 psi in the pressure cell and the temperature settingwere maintained, using computer control, until the end of thepolymerization experiment.

Preparation of the group 13 reagent and activator stock solutions: The“activator solution” is a 5 mM solution of N,N′-dimethylaniliniumtetrakis (pentafluorophenyl) borate in toluene (“ABF20”). The solutionis heated to approximately 85° C. to dissolve the reagent. The “group 13reagent” solution is either a 0.2 M solution ofdiisobutylaluminiumhydride (“DIBAL”) or a 0.2 M solution oftriethylboron (“BEt3”) or a 0.2 M solution of trimethylaluminium (“TMA”)or a solution that is 0.133 M in triethyl boron and 0.066M in diisobutylaluminium hydride (“DIBAL/BEt3”), all “group 13 reagent” solutions weresolutions in toluene.

Activation and Injection of solutions into the pressure reactor vessel:First, an appropriate amount of the 0.2 M group 13 reagent solution wasdispensed into a 1 mL vial that was kept at a constant premixtemperature as specified in the table 7. 0.100 mL (0.5 μmol) of themetal complex solution (5 mM in toluene) was added to the 1 mL vial.This mixture was held at a premix temperature for a time period of t₁ asindicated in table 7. Then, 0.110 mL (0.55 μmol) of the “activatorsolution” was added to the 1 mL vial. After the time period t₂ elapsed(time listed in table 7), a fraction of the total 1 mL vial contents(listed in table 7), followed immediately by approximately 0.3 mL oftoluene, were injected into the reaction vessel. The array ofexperiments with values for equivalents of group 13 reagent, t₁, t₂ andinjection fraction is described in table 7.

Polymerization: The polymerization reaction was allowed to continue fortimes shown in table 7A, during which time the temperature and pressurewere maintained at their pre-set levels by computer control. After thereaction time elapsed, the reaction was quenched by addition of anoverpressure of carbon dioxide sent to the reactor. The polymerizationtimes were the lesser of the maximum desired polymerization reactiontime or the time taken for a predetermined amount of monomer gas to beconsumed in the polymerization reaction.

Product work up: Propylene Polymerizations After the polymerizationreaction, the glass vial insert, containing the polymer product andsolvent, was removed from the pressure cell and removed from the inertatmosphere dry box, and the volatile components were removed using acentrifuge vacuum evaporator. After most of the volatile components hadevaporated, the vial contents were dried thoroughly by evaporation atelevated temperature under reduced pressure. The vial was then weighedto determine the yield of polymer product. The polymer product was thenanalyzed by rapid GPC, as described above to determine the molecularweight of the polymer produced, and by FTIR spectroscopy to determinethe crystallinity index. Results are presented in the tables 8-10.

TABLE 7 Description of array of polymerization experiments (examples11.A.1.-11.D.4.) group group 13 13 1 2 3 4 reagent^(a)) reagent^(b)) A C1 C 1 C 1 C 1 10 BEt3 DIBAL/ 20 BEt3 B C 1 C 1 C 1 C 1 10 TMA TMA C C 3C 3 C 3 C 3 10 BEt3 DIBAL/ 20 BEt3 D C 3 C 3 C 3 C 3 10 TMA TMA t₁ (min)10 0.5 10 0.5  t₂ (min) 0.5  10 0.5  0.5  Injection 0.066 0.066 0.0660.066 fraction Polym. 110  110  110  110  Temp (° C.) Premix 24 24 52 52Temp (° C.) Activator ABF20 ABF20 ABF20 ABF20 ^(a))Number of equivalentsand identity of group 13 reagent added to metal complex as described inactivation steps. ^(b))Group 13 reagent, which was placed in reactionvessel prior to catalyst injection (0.02 M solution was used).

TABLE 7A reaction times in seconds of experiments 11.A.1.-11.D.4. 1 2 34 A 490 601 601 600 B 214 217 264 213 C 406 601 555 374 D 208 243 264254

TABLE 8 Activity (mg polymer per minute per μmol) of examples11.A.1.-11.D.4. 1 2 3 4 A 320 198 253 254 B 864 877 648 780 C 503 319300 457 D 872 722 651 649

TABLE 9 Crystallinity index of examples 11.A.1.-11.D.4. 1 2 3 4 A 0.810.77 0.79 0.78 B 0.77 0.83 0.78 0.79 C 0.77 0.77 0.79 0.74 D 0.78 0.750.79 0.79

TABLE 10 Weight average molecular weight (k) of examples 11.A.1.-11.D.4.1 2 3 4 A 174 187 184 196 B 143 163 162 155 C 174 184 178 186 D 155 165168 167

Example 12 Propylene Polymerization Using Metal Complex 1 at DifferentPolymerization Temperatures

In this example, forty-eight polymerization reactions were carried out.The reactor was prepared as in Example 11, above. In addition, thepolymerization was run in the same manner and the polypropylene polymerwas worked up in the same manner as in Example 11, above.

Preparation of the group 13 reagent and activator stock solutions: The“activator solution” is a 5 mM solution of N,N′-dimethylaniliniumtetrakis (pentafluorophenyl) borate in toluene (“ABF20”) or a toluenesolution which is 5 mM in N,N′-dimethylaniliniumtertakis(pentafluorophenyl) borate and 10 mM in tris(pentafluorophenyl)borane (referred to in table 5 as“cocktail”). Both solutions are heatedto approximately 85° C. to dissolve the reagent. The group 13 reagentsolution is either a 0.2 M solution of diisobutylaluminiumhydride(“DIBAL”) or a 0.2 M solution of triethylboron (“BEt3”) or a 0.2 Msolution of triisobutylaluminium (“TIBA”) or a solution which is 0.133 Min triethyl boron and 0.033M in diisobutyl aluminium hydride(“DIBAL/BEt3”) or a solution which is 0.133 M in triethyl boron and0.066M in triisobutylaluminium (“TIBA/BEt3”).

Activation and Injection of solutions into the pressure reactor vessel:An appropriate amount based on the equivalents presented in table 11 ofa 0.2M solution of the group 13 reagent is dispensed into a 1 mL vial.0.100 mL of a 5 mM solution of metal complex 1 is added. After 9minutes, 0.110 mL solution of the “activator solution” in toluene wasadded to the 1 mL vial, with the appropriate activator solution beingidentified in table 11. About another 30 seconds later a fraction of thetotal 1 mL vial contents (with the fractional amount being identified intable 11, such that e.g., 0.2 refers to 20% by volume), followedimmediately by around 0.300 mL of toluene, were injected into thereaction vessel. The array of experiments is described in table 11. Thespecific times for each polymerization are shown in table 11a. Theresults are presented in tables 12-15.

TABLE 11 Description of polymerization experiments using Complex 1(examples 12.A.1-12.H.6): group 13 Group 13 1 2 3 4 5 6 reagent^(a))reagent^(b)) A C 1 C 1 C 1 C 1 C 1 C 1 30 DIBAL DIBAL B C 1 C 1 C 1 C 1C 1 C 1 10 DIBAL BEt₃ C C 1 C 1 C 1 C 1 C 1 C 1 10 DIBAL/ BEt₃ 20 BEt₃ DC 1 C 1 C 1 C 1 C 1 C 1 30 TIBA TIBA E C 1 C 1 C 1 C 1 C 1 C 1 10 TIBABEt₃ F C 1 C 1 C 1 C 1 C 1 C 1 10 TIBA/ BEt₃ 20 BEt₃ G C 1 C 1 C 1 C 1 C1 C 1 30 BEt₃ BEt₃ H C 1 C 1 C 1 C 1 C 1 C 1 60 BEt₃ BEt₃ Injection 0.20.2 0.2 0.1 0.2 0.2 Fraction Polym. 75 75 90 75 75 110 Temp. (° C.)Activator ABF20 ABF20 ABF20 ABF20 Cocktail Cocktail ^(a))Number ofequivalents and identity of group 13 reagent added to Metal Complex asdescribed in activation steps ^(b))Group 13 reagent, which was placed inreaction vessel prior of catalyst injection (0.02 M solution was used).

TABLE 11A polymerization times in seconds for examples 12.A.1.-12.H.6. 12 3 4 5 6 A 679 621 296 860 826 313 B 486 480 889 567 520 382 C 385 400472 378 608 225 D 902 901 612 901 901 901 E 900 900 901 901 901 901 F516 507 773 594 689 900 G 900 900 900 900 607 900 H 655 457 900 900 464900

TABLE 12 Activity (mg polymer per minute per μmol) of examples12.A.1.-12.H.6. 1 2 3 4 5 6 A 390 365 312 473 255 192 B 381 356 237 389195 150 C 681 605 420 1212 288 285 D 108 102 94 145 23 18 E 74 64 61 3420 47 F 403 378 231 588 157 37 G 62 80 n/d 10 158 4 H 176 396 208 36 2364 n/d: no data

TABLE 13 Crystallinity index of examples 12.A.1.-12.H.6. 1 2 3 4 5 6 A0.87 0.85 0.84 0.86 0.85 0.85 B 0.84 0.84 0.81 0.84 0.84 0.82 C 0.850.77 0.83 0.85 0.84 0.81 D 0.89 0.88 0.82 0.89 0.90 0.81 E 0.86 0.860.82 0.82 0.81 0.74 F 0.85 0.82 0.83 0.84 0.84 0.75 G 0.84 0.83 nd nd0.80 nd H 0.83 0.78 0.86 0.80 0.81 nd nd: not determined

TABLE 14 Weight average molecular weight (k) of examples 12.A.1.-12.H.6.1 2 3 4 5 6 A 1348 1356 708 1728 1419 166 B 2748 2934 1112 3852 4469 283C 1301 1437 714 2022 2844 214 D 2568 2381 1210 3011 2085 nd E 3819 40712109 3675 3944 331 F 2034 2179 1076 2678 3269 271 G 4641 4524 nd nd 4008nd H 3390 2858 1046 3059 3421 nd nd: not determined

TABLE 15 Melting points in ° C. of examples 12.A.1., 12.A.3., 12.A.6.,12.C.1., 12.C.3. and 12.C.6. 1 2 3 4 5 6 A 143 141 138 B C 140 139 137

Example 13 Ethylene/Styrene Copolymerization Using Metal Complexes

Twenty-three polymerization reactions were run with different metalcomplexes, temperatures, activators and activating conditions forcopolymerization of ethylene and styrene.

Preparation of the polymerization reactor prior to injection of catalystcomposition: A pre-weighed glass vial insert and disposable stirringpaddle were fitted to each reaction vessel of the reactor. The reactorwas then closed, 0.10 mL of a 0.02 M group 13 reagent solution intoluene and 3.8 mL of toluene were injected into each pressure reactionvessel through a valve (see table 16 for the reagents used). Theidentity of the group 13 reagent solution is given in table 16. Thetemperature was then set to 110° C., and the stirring speed was set to800 rpm, and the mixture was exposed to ethylene at 100 psi pressure. Anethylene pressure of 100 psi in the pressure cell and the temperaturesetting were maintained, using computer control, until the end of thepolymerization experiment.

Preparation of the group 13 reagent and activator stock solutions: The“activator solution” is a 5 mM solution of N,N′-dimethylaniliniumtetrakis (pentafluorophenyl) borate in toluene (“ABF20”). The solutionis heated to approximately 85° C. to dissolve the reagent. The group 13reagent solution is either a 0.2 M solution ofdiisobutylaluminiumhydride (“DIBAL”) or a 0.2 M solution oftrimethylaluminium (“TMA”), both in toluene.

Activation and Injection of solutions into the pressure reactor vessel:First, an appropriate amount of the 0.2 M group 13 reagent solution wasdispensed in a 1 mL vial which was kept at a constant premix temperatureas specified in the table 16. Then 0.100 mL of the metal complexsolution (5 mM in toluene) was added. This mixture was held at a premixtemperature for a time t₁ as indicated in table 16, during which time,0.420 mL of styrene followed immediately by 0.380 mL of toluene, wereinjected into the prepressurized reaction vessel. Then, 0.110 mL (0.55μmol) of the “activator solution” was added to the 1 mL vial. After thetime period t₂ elapsed, a fraction (as indicated in table 16) of thetotal 1 mL vial contents, followed immediately by approximately 0.3 mLof toluene were injected into the reaction vessel. The array ofexperiments is described in table 16.

Polymerization: The polymerization reaction was allowed to continue forthe 400-600 seconds, during which time the temperature and pressure weremaintained at their pre-set levels by computer control, with thespecific times for polymerization listed in table 16A. Thepolymerization times were the lesser of the maximum desiredpolymerization reaction time or the time taken for a predeterminedamount of monomer gas to be consumed in the polymerization reaction.After the reaction time elapsed, the reaction was quenched by additionof an overpressure of carbon dioxide.

Product work up: ethylene/styrene copolymerizations After thepolymerization reaction, the glass vial insert, containing the polymerproduct and solvent, was removed from the pressure cell and removed fromthe inert atmosphere dry box, and the volatile components were removedusing a centrifuge vacuum evaporator. After most of the volatilecomponents had evaporated, the vial contents were dried thoroughly byevaporation at elevated temperature under reduced pressure. The vial wasthen weighed to determine the yield of polymer product. The polymerproduct was then analyzed by rapid GPC, as described above to determinethe molecular weight of the polymer produced, and by FTIR spectroscopyto determine the styrene incorporation. Results are presented in thetables 17-19.

TABLE 16 Description of array of polymerization experiments examples13.A.1.-13.H.3. group 13 group 13 1 2 3 reagent^(a)) reagent^(b)) A C 1C 1 C 1 30 DIBAL DIBAL B C 1 C 1 10 DIBAL DIBAL C C 1 C 1 C 1 10 TMA TMAD C 3 C 3 C 3 10 DIBAL DIBAL E C 3 C 3 C 3 10 TMA TMA F C 2 C 2 C 2 30DIBAL DIBAL G C 2 C 2 C 2 10 DIBAL DIBAL H C 2 C 2 C 2 10 TMA TMA t₁(min) 10 10 0.8 t₂ (min) 0.5 0.5 0.5 Injection Fraction 0.2 0.2 0.2Premix Temp. (° C.) 24 50 50 Activator ABF20 ABF20 ABF20 ^(a))Number ofequivalents and identity of group 13 reagent added to Metal Complex asdescribed in activation steps ^(b))Group 13 reagent, which was placed inreaction vessel prior of catalyst injection (0.02 M solution was used).

TABLE 16A Polymerization times in seconds for 13.A.1.-13.H.3. 1 2 3 A601 602 444 B 601 601 n.d. C 601 600 601 D 602 601 553 E 601 602 600 F601 601 601 G 601 601 601 H 600 601 601 n.d.: not determined

TABLE 17 Activity (mg polymer per minute per μmol) of examples13.A.1.-13.H.3. 1 2 3 A 218 220 286 B 170 171 n.d. C 132 134 154 D 197193 240 E 145 151 166 F 209 215 217 G 174 176 193 H 144 147 151 n.d.:not determined

TABLE 18 Styrene incorporation (mol %) of examples 13.A.1.-13.H.3. 1 2 3A 2.4 3.0 3.0 B 3.0 3.8 n.d. C 2.9 3.0 3.0 D 3.9 3.8 3.7 E 3.2 2.7 2.9 F3.2 3.0 3.1 G 3.2 3.4 3.4 H 2.9 2.7 2.8 n.d.: not determined

TABLE 19 Weight average molecular weight (k) of examples 13.A.1.-13.H.3.1 2 3 A 228 241 247 B 386 371 n.d. C 480 484 534 D 275 276 361 E 461 521535 F 303 324 359 G 390 430 504 H 467 535 679 n.d.: not determined

Example 14 Preparation of Ligand/Metal Compositions and PropylenePolymerization with Ligand/Metal Compositions

Twenty-five polymerization reactions were carried out with differentligand/metal compositions, different temperatures, activators andactivation conditions for the polymerization of propylene. LigandsL1-L5, whose structures and synthesis are shown above, are used in thisexample.

In situ preparation of metal-ligand compositions: Stock solutions wereprepared as follows: The “metal precursor solution” is a 10 mM solutionof Hf(NMe₂)₄ in toluene. The “ligand solutions” are 25 mM solutions ofthe representative ligands in toluene, prepared in an array of 1 mLglass vials by dispensing 0.030 mL of a 25 mM ligand solution in a 1 mLglass vial. To each 1 mL glass vial containing ligand/toluene solutionwas added 0.075 mL of the metal precursor solution (0.75 μmol), to formthe metal-ligand combination solution. The reaction mixtures we allowedto sit at 80° C. for 2-3 hours during which time most of the solventevaporates. The reaction mixtures were then dried completely by blowinga stream of Argon over the 1 mL vial. Prior to addition of alkylationand activator solution, a small amount of solvent (0.020 mL) was addedto the dry composition.

Preparation of the polymerization reactor prior to injection of catalystcomposition: This part of this example was performed as described inExample 11, above.

Preparation of the group 13 reagent and activator stock solutions: The“activator solution” is a 5 mM solution of N,N′-dimethylaniliniumtetrakis (pentafluorophenyl) borate in toluene (“ABF20”). The solutionis heated to approximately 85° C. to dissolve the reagent. The group 13reagent solution is either a 0.2 M solution ofdiisobutylaluminiumhydride (“DIBAL”) or a 0.2 M solution oftriethylboron (“BEt3”) or a solution which is 0.133 M in triethyl boronand 0.066M in diisobutyl aluminium hydride (“DIBAL/BEt3”) or a solutionwhich is 0.133 M in triethyl boron and 0.066M in triisobutylaluminium(“TIBA/BEt3”).

Injection of solutions into the pressure reactor vessel: To the ligandmetal composition, 0.030 mL of a 500 mM solution of 1-octene in toluenethen 0.028 mL toluene and 0.112 mL of the group 13 reagent solution wasadded to the 1 mL vial. After 9 minutes, 0.165 mL (0.83 μmol) of the“activator solution” was added to the 1 mL vial. About another 30seconds later, 0.044 mL of the 1 mL vial contents, followed immediatelyby 0.356 mL of toluene, were injected into the reaction vessel. Thearray of experiments is described in detail in table 20.

Propylene Polymerizations and Product work up: This part of this examplewas performed as described in Example 11, above, with specificpolymerization times shown in table 20A. Results are presented in thetables 21-23.

TABLE 20 Description of array of polymerization experiments for examples14.A.1.-14.D.6. and 14.E.1. 1 2 3 4 5 6 A L1 L1 L1 L1 L1 L1 B L2 L2 L2L2 L2 L2 C L3 L3 L3 L3 L3 L3 D L4 L4 L4 L4 L4 L4 E L5 Polym. Temp. (°C.) 75 90 110 75 90 110 30 30  30 10/20 10/20 10/20 group 13reagent^(a)) DIBAL DIBAL DIBAL DIBAL/BEt3 DIBAL/BEt3 DIBAL/BEt3 group 13reagent^(b)) DIBAL DIBAL DIBAL BEt3 BEt3 BEt3 Activator ABF20 ABF20ABF20 ABF20 ABF20 ABF20 ^(a))Number of equivalents and identity of group13 reagent added to ligand metal combination as described in activationsteps. ^(b))Group 13 reagent, which was placed in reaction vessel priorof catalyst injection (0.02 M solution was used).

TABLE 20A Polymerization times in seconds of examples 14.A.1.-14.D.6.and 14.E.1. 1 2 3 4 5 6 A 263 138 901 250 160 215 B 578 253 901 522 372901 C 783 233 821 521 341 244 D 363 335 901 341 243 262 E 409

TABLE 21 Activity (mg polymer per minute per μmol) of examples14.A.1.-14.D.6. and 14.E.1. 1 2 3 4 5 6 A 710 635 41 900 786 256 B 103290 43 101 153 37 C 92 344 67 268 215 227 D 204 181 41 677 339 198 E 652

TABLE 22 Crystallinity index of examples 14.A.1.-14.D.6. and 14.E.1. 1 23 4 5 6 A 0.73 0.71 0.72 0.72 0.70 0.73 B 0.71 0.67 0.66 0.66 0.64 0.66C 0.76 0.70 0.70 0.70 0.65 0.68 D 0.80 0.77 0.79 0.78 0.76 0.80 E 0.76

TABLE 23 Weight average molecular weight (k) of examples 14.A.1.-14.D.6.and 14.E.1. 1 2 3 4 5 6 A 554 279 90 878 567 158 B 891 438 109 668 582112 C 1391 497 93 1136 488 95 D 803 489 106 980 661 149 E 463

Example 15 Preparation of Ligand/Metal Compositions and PropylenePolymerization with Ligand/Metal Compositions

Example 15.A.-15.F: Six polymerization reactions were carried out withdifferent ligand/metal compositions for the polymerization of propylene.Preparation of the polymerization reactor prior to injection of catalystcomposition, preparation of the stock solutions, propylenepolymerizations and product work up were performed as in Example 14. Theligands that were used are L4, L5 and L29 described above.

In situ preparation of metal-ligand compositions: Stock solutions wereprepared as follows: The “metal precursor solution” is a 10 mM solutionof Hf(NMe₂)₄ in toluene or a 10 mM solution of Zr(NMe₂)₄. The “ligandsolutions” are 25 mM solutions of the representative ligands in toluene,prepared in an array of 1 mL glass vials by dispensing 0.030 mL of a 25mM ligand solution in a 1 mL glass vial. To each 1 mL glass vialcontaining ligand/toluene solution was added 0.075 mL of the metalprecursor solution (0.75 μmol), to form the metal-ligand combinationsolution. The reaction mixtures we allowed to sit at 80° C. for 2-3hours during which time most of the solvent evaporates. The reactionmixtures were dried completely by blowing a stream of Argon over the 1mL vial. Prior to addition of alkylation and activator solution, a smallamount of solvent (0.020 mL) was added to the dry composition.

Injection of solutions into the pressure reactor vessel: To the ligandmetal composition, 0.037 mL of a 500 mM solution of 1-octene in tolueneand 0.020 mL toluene and 0.112 mL of the group 13 reagent solution wasadded to the 1 mL vial. After 9 minutes, 0.165 mL (0.083 μmol) of the“activator solution” was added to the 1 mL vial. About another 30seconds later, 0.090 mL of the 1 mL vial contents, followed immediatelyby 0.310 mL of toluene, were injected into the reaction vessel. Theresults are described in table 24.

Polymerization: The polymerization reaction was allowed to continue forthe 155-600 seconds, during which time the temperature and pressure weremaintained at their pre-set levels by computer control. Thepolymerization times were the lesser of the maximum desiredpolymerization reaction time or the time taken for a predeterminedamount of monomer gas to be consumed in the polymerization reaction. Thespecific times for each polymerization are shown in table 24. After thereaction time elapsed, the reaction was quenched by addition of anoverpressure of carbon dioxide.

Product work up: After the polymerization reaction, the glass vialinsert, containing the polymer product and solvent, was removed from thepressure cell and removed from the inert atmosphere dry box, and thevolatile components were removed using a centrifuge vacuum evaporator.After most of the volatile components had evaporated, the vial contentswere dried thoroughly by evaporation at elevated temperature underreduced pressure. The vial was then weighed to determine the yield ofpolymer product. The polymer product was then analyzed by rapid GPC, asdescribed above to determine the molecular weight of the polymerproduced, and by FTIR spectroscopy to determine crystallinity. Theresults are described in table 24.

TABLE 24 Results of examples 15.A and 15.F Polym. Melting Weight Temp.Metal time Cryst. point average Ligand (° C.) precursor (sec)Activity^(a)) Index^(b)) (° C.) % mmmm MW (k) A L4 75 Hf(NMe₂)₄ 301 3720.77 141 73 845 B L5 75 Hf(NMe₂)₄ 174 765 0.72 131 70 385 C L4 75Zr(NMe₂)₄ 308 80 0.74 129 nd 682 D L5 75 Zr(NMe₂)₄ 218 255 0.65 118 nd517 E L29 75 Hf(NMe₂)₄ 155 496 0.16 nd nd 288 F L29 75 Zr(NMe₂)₄ 600 180.19 nd nd 68 ^(a))Activity in mg polymer per minute per μmol;^(b))Crystallinity index by FTIR as described above nd: not determined

Example 16 Ethylene/1-Octene Copolymerization

Ten polymerization reactions were carried out with metal complex C 21described above at different activation conditions, for thecopolymerization of ethylene and 1-octene.

Preparation of the polymerization reactor prior to injection of catalystcomposition: A pre-weighed glass vial insert and disposable stirringpaddle were fitted to each reaction vessel of the reactor. The reactorwas then closed, 0.10 mL of a 0.02 M solution of group 13 reagents intoluene and 3.8 mL of toluene were injected into each pressure reactionvessel through a valve. The temperature was then set to 130° C. and thestirring speed was set to 800 rpm, and the mixture was exposed toethylene at 100 psi pressure. An ethylene pressure of 100 psi in thepressure cell and the temperature setting were maintained, usingcomputer control, until the end of the polymerization experiment. Theidentity of the of group 13 reagents is described in table 25.

Preparation of the group 13 reagent, activator stock solutions and metalcomplex solution: The “activator solution” is a 5 mM solution ofN,N′-dimethylanilinium tetrakis (pentafluorophenyl) borate in toluene(“ABF20”). The solution is heated to approximately 85° C. to dissolvethe reagent. The “group 13 reagent” solution is either a 0.20 M solutionof triisobutylaluminium (“TIBA”) or 0.20 M solution of triethylaluminium(“TEAL”) or a 0.20 M solution of trimethylaluminium (“TMA”) or 0.20 Msolution of diisobutylaluminiumhydride (“DIBAL”) or a 0.20 M solution oftriethylboron (“BEt₃”), all “group 13 reagent” solutions were solutionsin toluene. The metal complex solution is 5 mM solution of C21 intoluene (27.5 mg of C21 dissolved in 6.4 mL toluene).

Activation and Injection of solutions into the pressure reactor vessel:First, 0.016 mL of a 0.5 M solution of 1-octene in toluene was dispensedinto a 1 mL vial. Then, 0.060 mL (1.2 μmol) of the group 13 reagentsolution was dispensed into the 1 mL vial as specified in the table 25.Then, 0.080 ml (0.4 μmol) of the metal complex solution (5 mM intoluene) followed by 0.020 ml toluene was added to the 1 mL vial. Afteraround 9 min, 0.420 mL 1-octene, followed immediately by 0.380 mL oftoluene were injected into the reaction vessel. After another 30seconds, 0.088 mL (0.44 μmol) of the “activator solution” was added tothe 1 mL vial. After 30 seconds elapsed, a fraction of the total 1 mLvial contents (listed in table 25 as Catalyst injection fraction),followed immediately by approximately 0.7 mL of toluene, were injectedinto the reaction vessel. The array of experiments with values forequivalents and identity of group 13 reagent and injection fractions isdescribed in table 25.

Polymerization: The polymerization reaction was allowed to continue forthe time shown in table 25A, during which time the temperature andpressure were maintained at their pre-set levels by computer control.The polymerization times were the lesser of the maximum desiredpolymerization reaction time or the time taken for a predeterminedamount of monomer gas to be consumed in the polymerization reaction.After the reaction time elapsed, the reaction was quenched by additionof an overpressure of carbon dioxide sent to the reactor.

Product work up: ethylene/1-octene copolymerizations After thepolymerization reaction, the glass vial insert, containing the polymerproduct and solvent, was removed from the pressure cell and removed fromthe inert atmosphere dry box, and the volatile components were removedusing a centrifuge vacuum evaporator. After most of the volatilecomponents had evaporated, the vial contents were dried thoroughly byevaporation at elevated temperature under reduced pressure. The vial wasthen weighed to determine the yield of polymer product. The polymerproduct was then analyzed by rapid GPC, as described above to determinethe molecular weight of the polymer produced, and by FTIR spectroscopyto determine 1-octene incorporation. Results are presented in Table26-28.

TABLE 25 Description of array of polymerization experiments for examples16.A.1.- 16.E.2. 1 2 group 13 group 13 Polymerization temp (° C.) 130130 reagent^(a)) reagent^(b)) A C 21 C 21 30 TIBA TIBA B C 21 C 21 30DIBAL DIBAL C C 21 C 21 30 TMA TMA D C 21 C 21 30 TEAL TEAL E C 21 C 2130 BEt₃ BEt₃ Catalyst injection fraction  0.5  0.25 Activator ABF20ABF20 ^(a))Number of equivalents and identity of group 13 reagent addedto ligand metal combination as described in activation steps. ^(b))Group13 reagent, which was placed in reaction vessel prior of catalystinjection (0.02 M solution was used).

TABLE 25A Polymerization times in seconds of examples 16.A.1.-16.E.2. 12 A 350 457 B 278 349 C 311 457 D 169 466 E 601 600

TABLE 26 Activity (mg polymer per minute per μmol) of examples16.A.1.-16.E.2. 1 2 A 242 338 B 339 492 C 278 322 D 466 307 E 112 126

TABLE 27 wt % Octene incorporation of examples 16.A.1.-16.E.2. 1 2 A 3832 B 40 36 C 38 33 D 32 33 E 43 37

TABLE 28 Weight average molecular weight (k) of examples 16.A.1.-16.E.2.1 2 A 51 71 B 50 67 C 58 78 D 50 72 E 380 793

Example 17 Propylene Polymerization Using Metal Complex 7, 8, 9, 10 atDifferent Polymerization Temperatures

In this example, thirty-one polymerization reactions were carried out.The reactor was prepared as in Example 11, above. In addition, thepolymerization was run in the same manner and the polypropylene polymerwas worked up in the same manner as in Example 11, above.

Preparation of the polymerization reactor prior to injection of catalystcomposition: This part of this example was performed as described inExample 11, above.

Preparation of the group 13 reagent and activator stock solutions: The“activator solution” is a 5 mM solution of N,N′-dimethylaniliniumtetrakis (pentafluorophenyl) borate in toluene (“ABF20”). The solutionis heated to approximately 85° C. to dissolve the reagent. The “group 13reagent” solution is either a 0.2 M solution ofdiisobutylaluminiumhydride (“DIBAL”) or a 0.2 M solution oftrimethylaluminium (“TMA”). All “group 13 reagent” solutions weresolutions in toluene.

Activation and Injection of solutions into the pressure reactor vessel:First, an appropriate amount of the 0.2 M group 13 reagent solution wasdispensed into a 1 mL vial as specified in the table 29.0.100 mL (0.4μmol) of the metal complex solution (4 mM in toluene) was added to the 1mL vial. This mixture was held at at ambient temperature for a timeperiod of t₁ as indicated in table 29. Then, 0.088 mL (0.44 μmol) of the“activator solution” was added to the 1 mL vial. After the time periodt₂ elapsed (time listed in table 29), a fraction of the total 1 mL vialcontents (listed in table 29), followed immediately by approximately 0.3mL of toluene, were injected into the reaction vessel. The array ofexperiments with values for equivalents of group 13 reagent, t₁, t₂ andinjection fraction is described in table 29.

Polymerization: The polymerization reaction was allowed to continue forthe time shown in table 29A, during which time the temperature andpressure were maintained at their pre-set levels by computer control.The polymerization times were the lesser of the maximum desiredpolymerization reaction time or the time taken for a predeterminedamount of monomer gas to be consumed in the polymerization reaction.After the reaction time elapsed, the reaction was quenched by additionof an overpressure of carbon dioxide sent to the reactor.

Product work up: Propylene Polymerizations: This part of this examplewas performed as described in Example 11, above. The results arepresented in tables 30-32.

TABLE 29 Description of polymerization experiments using complexes 7-10(examples 17.A.1-17.H.3): 1 2 3 4 group 13 reagent^(a)) group 13reagent^(b)) A C7 C7 C7 C7 30 DIBAL B C7 C7 C7 C7 10 DIBAL C C8 C8 C8 C830 DIBAL D C8 C8 C8 C8 10 DIBAL E C9 C9 C9 C9 30 DIBAL F C9 C9 C9 C9 10DIBAL G C10 C10 C10 C10 30 DIBAL H C10 C10 C10 10 DIBAL t₁ (min) 10 1010 10 t₂ (min) 0.5 0.5 0.5 0.5 Injection Fraction 0.15 0.15 0.15 0.45Polym. Temp. (° C.) 90 90 110 130 group 13 reagent^(c)) DIBAL TMA DIBALDIBAL Activator ABF20 ABF20 ABF20 ABF20 ^(a))Number of equivalents ofgroup 13 reagent added to Metal Complex as described in activation steps^(b))Group 13 reagent, which was placed in reaction vessel prior ofcatalyst injection (0.02M solution was used). ^(c))Identity of group 13reagent added to Metal Complex as described in activation steps

TABLE 29A Polymerization times in seconds for examples 17.A1.-17.H.3. 12 3 4 A 346 178 288 661 B 291 150 341 900 C 272 145 266 902 D 251 141367 902 E 159 182 170 383 F 159 157 195 528 G 172 169 201 204 H 179 155196

TABLE 30 Activity (mg polymer per minute per μmol) of examples17.A.1.-17.H.3. 1 2 3 4 A 316 1020 320 49 B 416 1287 277 32 C 399 1254348 19 D 489 1496 240 21 E 989 1016 624 78 F 1006 1304 524 55 G 848 1250518 145 H 754 1495 507

TABLE 31 Crystallinity index of examples 17.A.1.-17.H.3. 1 2 3 4 A 0.910.87 0.84 0.88 B 0.88 0.88 0.89 0.89 C 0.86 0.82 0.84 0.83 D 0.85 0.820.84 0.86 B 0.86 0.86 0.86 0.88 F 0.85 0.83 0.84 0.87 G 0.83 0.86 0.860.91 H 0.87 0.87 0.85

TABLE 32 Weight average molecular weight (k) of examples 17.A.1.-17.H.3.1 2 3 4 A 536 350 161 32 B 552 310 175 50 C 579 422 218 44 D 859 345 23156 E 404 299 177 40 F 525 368 206 46 G 425 336 154 33 H 604 361 186 3

Example 18 Propylene Polymerization Using Metal Complex 11 (C 11) atDifferent Activation Methods

In this example, sixteen polymerization reactions were carried out. Thereactor was prepared as in Example 11, above. In addition, thepolymerization was run in the same manner and the polypropylene polymerwas worked up in the same manner as in Example 11, above.

Preparation of the polymerization reactor prior to injection of catalystcomposition: This part of this example was performed as described inExample 11, above.

Preparation of the group 13 reagent and activator stock solutions: The“activator solution” is a 2.5 mM solution of N,N′-dimethylaniliniumtetrakis (pentafluorophenyl) borate in toluene (“ABF20”). The solutionis heated to approximately 85° C. to dissolve the reagent. The “group 13reagent” solution is either a 0.05 M solution of triisobutylaluminium(“TIBA”) or 0.05 M solution of triethylaluminium (“TEAL”) or a 0.05 Msolution of trimethylaluminium (“TMA”) or 0.05 M solution ofdiisobutylaluminiumhydride (“DIBAL”) or a 0.05 M solution of AkzoPMAO-IP (“PMAO”) or 0.05M of Akzo MMAO-3A (“MMAO”), all “group 13reagent” solutions were solutions in toluene.

Activation and Injection of solutions into the pressure reactor vessel:First, an appropriate amount of the 0.05 M group 13 reagent solution wasdispensed into a 1 mL vial that was kept at a constant premixtemperature as specified in the table 33. Then, 0.100 mL (0.25 μmol) ofthe metal complex solution (2.5 mM in toluene) was added to the 1 mLvial. This mixture was held at a premix temperature for a time period oft₁ as indicated in table 33. Then, 0.110 mL (0.275 μmol) of the“activator solution” was added to the 1 mL vial. After the time periodt₂ elapsed, a fraction of the total 1 mL vial content, followedimmediately by approximately 0.3 mL of toluene, were injected into thereaction vessel. The array of experiments with values for equivalents ofgroup 13 reagent, t₁, t₂ and injection fraction is described in table33.

Polymerization: The polymerization reaction was allowed to continue forthe time shown in table 33A, during which time the temperature andpressure were maintained at their pre-set levels by computer control.The polymerization times were the lesser of the maximum desiredpolymerization reaction time or the time taken for a predeterminedamount of monomer gas to be consumed in the polymerization reaction.After the reaction time elapsed, the reaction was quenched by additionof an overpressure of carbon dioxide sent to the reactor.

Product work up: Propylene Polymerizations: This part of this examplewas performed as described in Example 11, above. The results arepresented in tables 34-36.

The array of experiments is described in table 33. The specific timesfor each polymerization are shown in table 33a. The results arepresented in tables 34-36.

TABLE 33 Description of polymerization experiments using complex 11(examples 18.A.1-18.H.2): group 13 group 13 1 2 reagent^(a))reagent^(b)) A C 11 C 11  6 TIBA TIBA B C 11 C 11  6 TEAL TEAL C C 11 C11  6 TMA TMA D C 11 C 11 10 TMA TMA E C 11 C 11  6 DIBAL DIBAL F C 11 C11 10 DIBAL DIBAL G C 11 C 11  6 PMAO-IP PMAO-IP H C 11 C 11  6 MMAOMMAO Injection Fraction  0.132  0.132 Polym. Temp. (° C.) 110 110 T₁(min)  10  0.5 T₂ (min)  0.5  0.5 Premix Temp. (° C.)  25  25 ActivatorABF20 ABF20 ^(a))Number of equivalents and identity of group 13 reagentadded to Metal Complex as described in activation steps ^(b))Group 13reagent, which was placed in reaction vessel prior of catalyst injection(0.02 M solution was used).

TABLE 33A Polymerization times in seconds for examples 18.A.1.-18.H.2. 12 A 241 279 B 236 199 C 263 226 D 303 223 E 257 601 F 242 601 G 199 231H 232 186

TABLE 34 Activity (mg polymer per minute per μmol) of examples18.A.1.-18.H.2. 1 2 A 782 577 B 741 959 C 663 794 D 533 831 E 714 224 F714 160 G 930 842 H 741 1050

TABLE 35 Crystallinity index of examples 18.A.1.-18.H.2. 1 2 A 0.87 0.88B 0.87 0.87 C 0.87 0.86 D 0.86 0.88 E 0.89 0.85 F 0.87 0.84 G 0.89 0.81H 0.88 0.84

TABLE 36 Weight average molecular weight (k) of examples 18.A.1.-18.H.2.1 2 A 80 81 B 86 94 C 101 105  D 101 n.d. B 77 n.d. F 75 70 G 109 n.d. H107 106  n.d. not determined

Example 19 Propylene Polymerization Using Metal Complex 1, 2, 9, 12, 13,14, 15 and 16

In this example, eight polymerization reactions were carried out. Thereactor was prepared as in Example 11, above.

Preparation of the polymerization reactor prior to injection of catalystcomposition: This part of this example was performed as described inExample 11, above.

Preparation of the group 13 reagent and activator stock solutions: The“activator solution”is a 5 mM solution of N,N′-dimethylaniliniumtetrakis (pentafluorophenyl) borate in toluene (“ABF20”). The solutionis heated to approximately 85° C. to dissolve the reagent. The “group 13reagent” solution a 0.2 M solution of trimethylaluminium (“TMA”), all“group 13 reagent” solutions were solutions in toluene.

Activation and Injection of solutions into the pressure reactor vessel:First, 0.120 mL (0.6 μmol) of the metal complex solution (5 mM intoluene) was added to the 1 mL vial. Then, 0.012 ml of a 0.5 M solutionof 1-octene intoluene followed by 0.090 ml of the 0.2 M group 13 reagentsolution was dispensed into a 1 mL as specified in the table 37. Thismixture was held for a time period of t₁ as indicated in table 37. Then,0.132 mL (0.66 μmol) of the “activator solution” was added to the 1 mLvial. After the time period t₂ elapsed (time listed in table 37), afraction of the total 1 mL vial contents (listed in table 37), followedimmediately by approximately 0.3 mL of toluene, were injected into thereaction vessel. The array of experiments with values for equivalents ofgroup 13 reagent, t₁, t₂ and injection fraction is described in table37.

Polymerization: The polymerization reaction was allowed to continue forthe time shown in table 37A, during which time the temperature andpressure were maintained at their pre-set levels by computer control.The polymerization times were the lesser of the maximum desiredpolymerization reaction time or the time taken for a predeterminedamount of monomer gas to be consumed in the polymerization reaction.After the reaction time elapsed, the reaction was quenched by additionof an overpressure of carbon dioxide sent to the reactor.

Product work up: Propylene Polymerizations: This part of this examplewas performed as described in Example 11, above. The results arepresented in tables 38-40.

TABLE 37 Description of polymerization experiments using complexes 1, 2,9, 12, 13, 14, 15 and 16 (examples 19.A.1-19.H.1): 1 Group 13reagent^(b)) A C 13 TMA B C 14 TMA C C 15 TMA D C 16 TMA B C 12 TMA F C9 TMA G C 1 TMA H C 2 TMA Injection Fraction  0.10 Polym. Temp. (° C.)110 Group 13 reagent^(a)) 30 TMA t₁ (min)  10 t₂ (min)  0.5 ActivatorABF20 ^(a))Number of equivalents and identity of group 13 reagent addedto Metal Complex as described in activation steps ^(b))Group 13 reagent,which was placed in reaction vessel prior of catalyst injection (0.02 Msolution was used).

TABLE 37A Polymerization times in seconds for examples 19.A.1-19.H.1. 1A 431 B 224 C 900 D 900 E 94 F 174 G 165 H 86

TABLE 38 Activity (mg polymer per minute per μmol) of examples19.A.1-19.H.1. 1 A 230 B 716 C 79 D 47 E 2511 F 825 G 779 H 1466

TABLE 39 Crystallinity index of examples 19.A.1-19.H.1. 1 A 0.38 B 0.56C 0.53 D 0.30 E 0.92 F 0.91 G 0.88 H 0.88

TABLE 40 Weight average molecular weight (k) of examples 19.A.1-19.H.1.1 A 64 B 94 C 67 D 76 E 86 F 100 G 90 H 89

Example 20 Propylene Polymerization Using Metal Complexes 9 and 12 atDifferent Polymerization Temperatures

In this example, four polymerization reactions were carried out.

Preparation of the polymerization reactor prior to injection of catalystcomposition: This part of this example was performed as described inExample 11, above.

Preparation of the group 13 reagent and activator stock solutions: The“activator solution” is a 5 mM solution of N,N′-dimethylaniliniumtetrakis (pentafluorophenyl) borate in toluene (“ABF20”). The solutionis heated to approximately 85° C. to dissolve the reagent. The “group 13reagent” solution a 0.2 M solution of diisobutylaluminiumhydride(“DIBAL”), all “group 13 reagent” solutions were solutions in toluene.

Activation and Injection of solutions into the pressure reactor vessel:First, an appropriate amount of the 0.2 M group 13 reagent solution wasdispensed into a 1 mL vial as specified in the table 41. 0.120 mL (0.6μmol) of the metal complex solution (5 mM in toluene) was added to the 1mL vial. This mixture was held at a premix temperature for a time periodof t₁ as indicated in table 41. Then, 0.132 mL (0.66 μmol) of the“activator solution” was added to the 1 mL vial. After the time periodt₂ elapsed (time listed in table 41), a fraction of the total 1 mL vialcontents (listed in table 41), followed immediately by approximately 0.3mL of toluene, were injected into the reaction vessel. The array ofexperiments with values for equivalents of group 13 reagent, t1, t2 andinjection fraction is described in table 41.

Polymerization: The polymerization reaction was allowed to continue for120-900 seconds, during which time the temperature and pressure weremaintained at their pre-set levels by computer control. The specifictimes for each polymerization are shown in table 41a. After the reactiontime elapsed, the reaction was quenched by addition of an overpressureof carbon dioxide sent to the reactor.

Product work up: Propylene Polymerizations: This part of this examplewas performed as described in Example 11, above. The results arepresented in tables 42-45

TABLE 41 Description of polymerization experiments using complexes 9 and12 (examples 20.A.1-20.B.2): group 13 group 13 1 2 reagent^(a))reagent^(b)) A C 9 C 9 30 DIBAL DIBAL B C 12 C 12 30 DIBAL DIBALInjection Fraction 0.075 0.20 Polym. Temp. (° C.) 110 130 T₁ (min) 10 10T₂ (min) 0.5 0.5 Activator ABF20 ABF20 ^(a))Number of equivalents andidentity of group 13 reagent added to Metal Complex as described inactivation steps ^(b))Group 13 reagent, which was placed in reactionvessel prior of catalyst injection (0.02M solution was used).

TABLE 41A Polymerization times in seconds for examples 20.A.1-20.B.2 1 2A 215 900 B 120 901

TABLE 42 Activity (mg polymer per minute per μmol) of examples20.A.1-20.B.2 1 2 A  603 37 B 1232 49

TABLE 43 Crystallinity index of examples 20.A.1-20.B.2 1 2 A 0.86 0.86 B0.83 0.78

TABLE 44 Melting points of examples (in ° C.) 20.A.1-20.B.2 1 2 A145/152 138/147 B 137/144 133/141 Bimodal melting points observed

TABLE 45 Weight average molecular weight (k) of examples 20.A.1-29.B.2 12 A 94 26 B 59 15

Example 21 Preparation of Ligand/Metal Compositions and PropylenePolymerization with Ligand/Metal Compositions

Twenty-four polymerization reactions were carried out with differentligand/metal compositions, different temperatures, activators andactivation conditions for the polymerization of propylene. Ligands 6-13,whose structures and synthesis are shown above, are used in thisexample.

In situ preparation of metal-ligand compositions: This part of thisexample was performed as described in Example 14, above.

Preparation of the polymerization reactor prior to injection of catalystcomposition: This part of this example was performed as described inExample 11, above.

Preparation of the group 13 reagent and activator stock solutions: The“activator solution” is a 5 mM solution of N,N′-dimethylaniliniumtetrakis (pentafluorophenyl) borate in toluene (“ABF20”). The solutionis heated to approximately 85° C. to dissolve the reagent. The group 13reagent solution is a 0.2 M solution of diisobutylaluminiumhydride(“DIBAL”).

Injection of solutions into the pressure reactor vessel: To the ligandmetal composition, 0.030 mL of a 500 mM solution of 1-octene in tolueneand 0.028 ml of toluene and 0.112 mL of the group 13 reagent solutionwas added to the 1 mL vial. After 9 minutes, 0.165 mL (0.83 μmol) of the“activator solution” was added to the 1 mL vial. About another 30seconds later, a fraction of the total 1 mL vial contents (listed intable 46 as Injection fractio), followed immediately by approximately0.3 mL of toluene, were injected into the reaction vessel. The array ofexperiments is described in detail in table 46.

Propylene Polymerizations and Product work up: This part of this examplewas performed as described in Example 11, above, with specificpolymerization times shown in table 51A. Results are presented in thetables 47-50.

Propylene Polymerizations and Product work up: This part of this examplewas performed as described in Example 11, above, with specificpolymerization times shown in table 46A. Results are presented in thetables 47-50.

TABLE 46 Description of array of polymerization experiments for examples21.A.1.-21.H.3. 1 2 3 A L10 L10 L10 B L11 L11 L11 C L12 L12 L12 D L13L13 L13 E L6 L6 L6 F L7 L7 L7 G L8 L8 L8 H L9 L9 L9 group 13reagent^(a)) 30 DIBAL 30 DIBAL 30 DIBAL group 13 reagent ^(b)) DIBALDIBAL DIBAL Activator ABF20 ABF20 ABF20 Polym. Temp (° C.): 90 110 130Injection fraction 0.086 0.13 0.26 ^(a))Number of equivalents andidentity of group 13 reagent added to ligand metal combination asdescribed in activation steps. ^(b))Group 13 reagent, which was placedin reaction vessel prior of catalyst injection (0.02M solution wasused).

TABLE 46A Polymerization times in seconds of examples 21.A.1.-21.H.3. 12 3 A 901 901 901 B 900 901 901 C 900 901 900 D 901 901 901 E 252 327901 F 359 902 901 G 288 287 900 H 155 229 900

TABLE 47 Activity (mg polymer per minute per μmol) of examples 21.A.1.-21.H.3. 1 2 3 A 12 3 1 B 10 2 1 C 1 1 0 D 23 6 2 E 429 158 18 F 250 5010 G 329 191 15 H 853 258 20

TABLE 48 Crystallinity index of examples 21.A.1.- 21.H.3. 1 2 3 A n.d.n.d. n.d. B n.d. n.d. n.d. C n.d. n.d. n.d. D 0.74 n.d. n.d. E 0.85 0.840.81 F 0.89 0.84 0.86 G 0.84 0.87 0.82 H 0.80 0.86 0.84 n.d. = notdetermined

TABLE 49 Weight average molecular weight (k) of examples 21.A.1.-21.H.3.1 2 3 A n.d. n.d. n.d. B n.d. n.d. n.d. C n.d. n.d. n.d. D 310 n.d. n.d.E 681 165 30 F 537 106 19 G 560 124 25 H 458 124 26 n.d. = notdetermined

TABLE 50 Melting points of selected examples (in ° C.) 21.E.1., 21.F.1.and 21.H.1. 1 2 3 A B C D E 142/147 F 148 G H 146 Bimodal melting pointsdetected

Example 22 Preparation of Ligand/Metal Compositions and PropylenePolymerization with Ligand/Metal Compositions

Eighteen polymerization reactions were carried out with differentligand/metal compositions, different temperatures, activators andactivation conditions for the polymerization of propylene. LigandsL14-L19, whose structures and synthesis are shown above, are used inthis example.

In situ preparation of metal-ligand compositions: This part of thisexample was performed as described in Example 14, above.

Preparation of the polymerization reactor prior to injection of catalystcomposition: This part of this example was performed as described inExample 11, above.

Preparation of the group 13 reagent and activator stock solutions: The“activator solution” is a 5 mM solution of N,N′-dimethylaniliniumtetrakis pentafluorophenyl) borate in toluene (“ABF20”). The solution isheated to approximately 85° C. to dissolve the reagent. The group 13reagent solution is a 0.2 M solution of diisobutylaluminiumhydride(“DIBAL”).

Injection of solutions into the pressure reactor vessel: To the ligandmetal composition, 0.030 mL of a 500 mM solution of 1-octene in tolueneand 0.112 mL of the group 13 reagent solution was added to the 1 mLvial. After 9 minutes, 0.165 mL (0.83 μmol) of the “activator solution”was added to the 1 mL vial. About another 30 seconds later, a fractionof the total 1 mL vial contents (listed in table 51), followedimmediately by approximately 0.3 mL of toluene, were injected into thereaction vessel. The array of experiments is described in detail intable 51.

Propylene Polymerizations and Product work up: This part of this examplewas performed as described in Example 11, above, with specificpolymerization times shown in table 51A. Results are presented in thetables 52-55.

TABLE 51 Description of array of polymerization experiments for examples22.A.1.- 22.F.3. 1 2 3 A L14 L14 L14 B L15 L15 L15 C L16 L16 L16 D L17L17 L17 E L18 L18 L18 F L19 L19 L19 Polym. Temp (° C.): 90 110 130 group13 reagent^(a)) 30 DIBAL 30 DIBAL 30 DIBAL group 13 reagent^(b)) DIBALDIBAL DIBAL Activator ABF20 ABF20 ABF20 Injection fraction  0.065  0.13 0.26 ^(a))Number of equivalents and identity of group 13 reagent addedto ligand metal combination as described in activation steps. ^(b))Group13 reagent, which was placed in reaction vessel prior of catalystinjection (0.02 M solution was used).

TABLE 51A Polymerization times in seconds of examples 22.A.1.-22.F.3. 12 3 A 900 902 901 B 901 901 900 C 224 290 901 D n.d. 902 901 E 518 901901 F 538 901 901 n.d. = not determined

TABLE 52 Activity (mg polymer per minute per μmol) of examples22.A.1.-22.F.3. 1 2 3 A 2 1 1 B 9 2 1 C 556 188 14 D n.d. 1 1 E 203 33 6F 195 21 6 n.d. = not determined

TABLE 53 Crystallinity index of examples examples 22.A.1.-22.F.3. 1 2 3A n.d. n.d. n.d. B n.d. n.d. n.d. C 0.48 0.52 0.47 D n.d. n.d. n.d. E0.54 0.56 n.d. F 0.60 0.61 n.d. n.d. = not determined

TABLE 54 Weight average molecular weight (k) of examples 22.A.1.-22.F.3.1 2 3 A n.d. n.d. n.d. B n.d. n.d. n.d. C 334 97 18 D n.d. n.d. n.d. E229 62 n.d. F 248 46 n.d. n.d. = not determined

TABLE 55 Melting points (in ° C.) of selected examples for22.A.1.-22.F.3. 1 2 3 A B C 118 D E 130/139 F 134/141 Bimodal meltingpoints detected

Example 23 Ethylene-Styrene Copolymerization Using Metal Complexes 7, 8,9 and 10 (C7, C8, C9, C10) at Different Activation Conditions

Twenty-four polymerization reactions were run with different metalcomplexes, temperatures, activators and activating conditions forcopolymerization of ethylene and styrene.

Preparation of the polymerization reactor prior to injection of catalystcomposition: A pre-weighed glass vial insert and disposable stirringpaddle were fitted to each reaction vessel of the reactor. The reactorwas then closed, 0.10 mL of a 0.02 M group 13 reagent solution intoluene and 3.8 mL of toluene were injected into each pressure reactionvessel through a valve. The identity of the group 13 reagent solution isgiven in table 56. The temperature was then set to the appropriatepolymerization temperature (as described in table 56), and the stirringspeed was set to 800 rpm, and the mixture was exposed to ethylene at 100psi pressure. An ethylene pressure of 100 psi in the pressure cell andthe temperature setting were maintained, using computer control, untilthe end of the polymerization experiment.

Preparation of the group 13 reagent and activator stock solutions: The“activator solution” is a 5 mM solution of N,N′-dimethylaniliniumtetrakis (pentafluorophenyl) borate in toluene (“ABF20”). The solutionis heated to approximately 85° C. to dissolve the reagent. The group 13reagent solution is either a 0.2 M solution ofdiisobutylaluminiumhydride (“DIBAL”) or a 0.2 M solution oftrimethylaluminium (“TMA”), both in toluene.

Activation and Injection of solutions into the pressure reactor vessel:First, an appropriate amount of the 0.2 M group 13 reagent solution wasdispensed in a 1 mL vial which was kept at a constant premix temperatureas specified in the table 56. Then 0.100 mL of the metal complexsolution (4 mM in toluene) was added. This mixture was held at a premixtemperature for a time t₁ as indicated in table 56, during which time,0.420 mL of styrene followed immediately by 0.380 mL of toluene, wereinjected into the prepressurized reaction vessel. Then, 0.088 mL (0.55μmol) of the “activator solution” was added to the 1 mL vial. After thetime period t₂ elapsed, a fraction (as indicated in table 56) of thetotal 1 mL vial contents, followed immediately by approximately 0.3 mLof toluene were injected into the reaction vessel. The array ofexperiments is described in table 56.

Polymerization: The polymerization reaction was allowed to continue forthe the time shown in table 56A, during which time the temperature andpressure were maintained at their pre-set levels by computer control.The polymerization times were the lesser of the maximum desiredpolymerization reaction time or the time taken for a predeterminedamount of monomer gas to be consumed in the polymerization reaction.After the reaction time elapsed, the reaction was quenched by additionof an overpressure of carbon dioxide.

Product work up: ethylene/styrene copolymerizations After thepolymerization reaction, the glass vial insert, containing the polymerproduct and solvent, was removed from the pressure cell and removed fromthe inert atmosphere dry box, and the volatile components were removedusing a centrifuge vacuum evaporator. After most of the volatilecomponents had evaporated, the vial contents were dried thoroughly byevaporation at elevated temperature under reduced pressure. The vial wasthen weighed to determine the yield of polymer product. The polymerproduct was then analyzed by rapid GPC, as described above to determinethe molecular weight of the polymer produced, and by FTIR spectroscopyto determine the styrene incorporation. Results are presented in thetables 57-59.

TABLE 56 Description of polymerization experiments using complexes 7-10for examples 23.A.1-23.H.3. 1 2 3 group 13 reagent^(a)) A C 7 C 7 C 7 30B C 7 C 7 C 7 10 C C 8 C 8 C 8 30 D C 8 C 8 C 8 10 E C 9 C 9 C 9 30 F C9 C 9 C 9 10 G C 10 C 10 C 10 30 H C 10 C 10 C 10 10 Injection Fraction 0.25  0.25  0.25 Polym. Temp. (° C.) 110 110 110 Premix temp. (° C.) 24  50  50 group 13 reagent^(c)) DIBAL DIBAL TMA group 13 reagent^(b))DIBAL DIBAL TMA Activator ABF20 ABF20 ABF20 ^(a))Number of equivalentsof group 13 reagent added to Metal Complex as described in activationsteps ^(b))Group 13 reagent, which was placed in reaction vessel priorof catalyst injection (0.02 M solution was used). c)Identity of group 13reagent added to Metal Complex as described in activation steps

TABLE 56A Polymerization times in seconds for examples 23.A.1.-23.H.3. 12 3 A 720 337 305 B 901 749 900 C 353 259 284 D 900 840 902 E 760 265281 F 902 901 901 G 582 300 492 H 902 902 883

TABLE 57 Activity (mg polymer per minute per μmol) of examples23.A.1.-23.H.3. 1 2 3 A 186 386 453 B 129 180 126 C 346 457 413 D 122155 117 E 188 524 492 F 127 139 129 G 244 467 276 H 125 144 143

TABLE 58 Styrene incorporation (mol %) of examples 23.A.1.-23.H.3. 1 2 3A 3.1 3.7 3.6 B 3.8 4.5 4.9 C 2.5 3.1 2.9 D 2.8 3.6 3.7 E 3.5 4.1 3.5 F3.9 4.6 4.4 G 3.1 3.8 3.3 H 3.9 4.8 4.3

TABLE 59 Weight average molecular weight (k) of examples 23.A.1.-23.H.3.1 2 3 A 322 255 311 B 512 571 987 C 334 253 233 D 530 384 577 E 645 270274 F 464 652 762 G 301 214 256 H 176 512 743

Example 24 Ethylene-Styrene Copolymerization Using Metal Complexes 17,18, 19 and 20 (C17, C18, C19, C20) at Different Activation Conditions

Sixteen polymerization reactions were run with different metal complexesand activating conditions for copolymerization of ethylene and styrene.

Preparation of the polymerization reactor prior to injection of catalystcomposition: A pre-weighed glass vial insert and disposable stirringpaddle were fitted to each reaction vessel of the reactor. The reactorwas then closed, 0.050 mL of a 0.02 M group 13 reagent solution intoluene and 4.55 mL of toluene were injected into each pressure reactionvessel through a valve. The identity of the group 13 reagent solution isgiven in table 60. The temperature was then set to 110° C., and thestirring speed was set to 600 rpm, and the mixture was exposed toethylene at 100 psi pressure. An ethylene pressure of 100 psi in thepressure cell and the temperature setting were maintained, usingcomputer control, until the end of the polymerization experiment.

Preparation of the group 13 reagent and activator stock solutions: The“activator solution” is a 5 mM solution of N,N′-dimethylaniliniumtetrakis (pentafluorophenyl) borate in toluene (“ABF20”). The solutionis heated to approximately 85° C. to dissolve the reagent. The group 13reagent solution is a 0.2 M solution of triisobutylaluminium (“TIBA”).

Activation and Injection of solutions into the pressure reactor vessel:First, 0.200 mL of the metal complex solution (5 mM in toluene) wasdispensed in a 1 mL vial. Then, an appropriate amount of the 0.2 M group13 reagent solution was added. This mixture was held for 75 seconds,during which time, 0.500 mL of styrene followed immediately by 0.500 mLof toluene, and 0.100 mL of the “activator solution” followedimmediately by 0.400 mL of toluene were injected into the prepressurizedreaction vessel. Then, half of the total 1 mL vial contents, followedimmediately by approximately 0.3 mL of toluene were injected into thereaction vessel. The array of experiments is described in table 60.

Polymerization: The polymerization reaction was allowed to continue forthe times shown in table 60A, during which time the temperature andpressure were maintained at their pre-set levels by computer control.The polymerization times were the lesser of the maximum desiredpolymerization reaction time or the time taken for a predeterminedamount of monomer gas to be consumed in the polymerization reaction.After the reaction time elapsed, the reaction was quenched by additionof an overpressure of carbon dioxide.

Product work up: ethylene/styrene copolymerizations: This part of thisexample was performed as described in example 23. Results are presentedin the tables 61-63.

TABLE 60 Description of polymerization experiments using complexes 7-10(examples 24.A.1-24.H.2): 1 2 A C 17 C 17 B C 17 C 17 C C 18 C 18 D C 18C 18 E C 19 C 19 F C 19 C 19 G C 20 C 20 H C 20 C 20 Polym. Temp. (° C.)110 110 group 13 reagent^(c) 5 TIBA 10 TIBA group 13 reagent^(b)) TIBATIBA Activator ABF20 ABF20 ^(a)Number of equivalents and identity ofgroup 13 reagent added to Metal Complex as described in activation steps^(b))Group 13 reagent, which was placed in reaction vessel prior ofcatalyst injection (0.02 M solution was used).

TABLE 60A Polymerization times in seconds for examples 24.A.1-24.H.2 1 2A 900 900 B 900 900 C 900 900 D 900 900 E 639 408 F 670 464 G 900 743 H900 797

TABLE 61 Activity (mg polymer per minute per μmol) of examples24.A.1-24.H.2 1 2 A 21 23 B 22 22 C 20 23 D 21 22 E 43 61 F 41 57 G 2844 H 29 41

TABLE 62 Styrene incorporation (mol %) of examples 24.A.1-24.H.2 1 2 A3.1 3.3 B 3.2 3.4 C 4.3 3.6 D 3.6 3.8 E 3.9 3.3 F 4.1 3.3 G 5.5 4.7 H5.2 5.1

TABLE 63 Weight average molecular weight (k) of examples 24.A.1-24.H.2 12 A 50 42 B 62 36 C 79 34 D 80 47 E 118 49 F 116 52 G 549 259 H 422 226

It is to be understood that the above description is intended to beillustrative and not restrictive. Many embodiments will be apparent tothose of skill in the art upon reading the above description. The scopeof the invention should, therefore, be determined not with reference tothe above description, but should instead be determined with referenceto the appended claims, along with the full scope of equivalents towhich such claims are entitled. The disclosures of all articles andreferences, including patent applications and publications, areincorporated herein by reference for all purposes.

What is claimed is:
 1. A process for the production of anethylene-isobutylene copolymer, comprising forming a reaction mixture ofat least ethylene, isobutylene and a catalyst and subjecting thereaction mixture to polymerization conditions, wherein said catalystcomprises: (1) a ligand represented by the general formula:

 wherein R¹ is selected from the group consisting of aryl andsubstituted aryl; T is —Cr²R³— and R² are R³ are independently selectedfrom the group consisting of hydrogen, alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, heteroalkyl, substitutedheteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl,silyl, boryl, phosphino, amino, thio, seleno, halide, nitro, andcombinations thereof; and optionally, any combination of R¹, R², and R³may be joined together in a ring structure; R⁴, R⁵, R⁶ and R⁷ are eachhydrogen; (2) a metal precursor compound characterized by the generalformula Hf(L)_(n) wherein each L is independently selected from thegroup consisting of halide, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, substituted heteroalkyl,heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxy, aryloxy, hydroxy, boryl,silyl, amino, amine, hydrido, allyl, diene, seleno, phosphino,phosphine, carboxylates, thio, 1,3-dionates, oxalates, carbonates,nitrates, sulphates, ethers, thioethers and combinations thereof oroptionally two or more L groups are joined into a ring structure; n is1, 2, 3, 4, 5, or 6; (3) optionally, at least one activator; and (4)optionally, a trialkyl aluminum compound.
 2. A process of claim 1,wherein said polymerization wherein R³ is selected from the groupconsisting of substituted alkyl, aryl and substituted aryl.
 3. Theprocess of claim 2, wherein a trialkyl aluminum compound is present. 4.The process of claim 3, wherein said said trialkyl aluminum compound istriethylaluminum.
 5. The process of claim 3, wherein saidtriethylaluminum is present in an amount of at least 0.1 equivalents tothe metal precursor compound.
 6. The process of claim 3 wherein saidtriethylaluminum is present in an amount of between 1 and 10 equivalentsto the metal precursor compound.
 7. The process of claim 1, wherein anactivator is present.
 8. The process of claim 5, wherein said activatoris an ion forming compound comprising boron.
 9. The process of claim 1,wherein said ligand is selected from the group consisting of:


10. The process of claim 1, wherein the ligand is mixed with the metalprecursor prior to, or while contacting said ethylene and isobutylene.